WO2010032600A1 - 接着剤組成物及びこれからなる接着剤 - Google Patents
接着剤組成物及びこれからなる接着剤 Download PDFInfo
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- WO2010032600A1 WO2010032600A1 PCT/JP2009/065048 JP2009065048W WO2010032600A1 WO 2010032600 A1 WO2010032600 A1 WO 2010032600A1 JP 2009065048 W JP2009065048 W JP 2009065048W WO 2010032600 A1 WO2010032600 A1 WO 2010032600A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
- C09J123/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the present invention relates to an adhesive composition
- a soft polypropylene resin composition (X) in which a propylene copolymer (A) having a specific physical property parameter and a crystalline isotactic polypropylene (B) are formed in a specific ratio
- the present invention relates to an adhesive comprising the composition.
- the present invention relates to an adhesive technique that is excellent in handling during use.
- Polymers called base polymers are used for hot melt adhesives that are attracting attention as solventless adhesives that do not generate VOCs.
- Examples of such a base polymer include ethylene-vinyl acetate copolymer (EVA) and ethylene / ⁇ -olefin copolymer such as ethylene-based copolymer, amorphous polyolefin (APAO), and styrene elastomer ( SBS, SIS, SEBS, SEPS) and the like are known.
- a base polymer for example, ethylene / vinyl acetate copolymer (EVA) or ethylene / ⁇ -olefin copolymer which is excellent in flexibility but inferior in heat resistance and rubber elasticity, in flexibility and rubber elasticity.
- EVA ethylene / vinyl acetate copolymer
- ethylene / ⁇ -olefin copolymer which is excellent in flexibility but inferior in heat resistance and rubber elasticity, in flexibility and rubber elasticity.
- Styrenic elastomers SIS, SBS
- APAO amorphous polyolefins
- SEBS is also known as a material having a relatively excellent performance balance. However, when used in a harsh environment, heat resistance is sometimes insufficient.
- soft polypropylene polymers having excellent heat resistance
- the feature of these soft polypropylene polymers is that they use a material having a narrow molecular weight distribution and composition distribution by using a specific catalyst such as a metallocene catalyst.
- a specific catalyst such as a metallocene catalyst.
- known products having a wide molecular weight distribution and a wide composition distribution such as It is disclosed that it has performance superior to that of APAO (for example, there is no deterioration in adhesion performance due to a low molecular weight component and no deterioration in workability due to a high molecular weight component).
- Patent Document 1 discloses a technique for obtaining a hot melt adhesive using a copolymer of propylene and ethylene. Such a propylene / ethylene copolymer has excellent flexibility, rubber elasticity, and heat resistance stability, but has insufficient heat resistance and creep resistance characteristics when subjected to stress at high temperatures.
- the document also discloses a technique for blending a crystalline isotactic polypropylene component to improve heat resistance. According to the knowledge of the present inventors, propylene / ethylene copolymer is compatible with polypropylene. Therefore, it is considered that sufficient heat resistance improvement effect cannot be obtained.
- Patent Document 2 discloses a technique for obtaining a hot melt adhesive using a soft polypropylene polymer that is softened by controlling the stereoregularity of the propylene chain.
- a soft polypropylene polymer is considered to have better compatibility with crystalline isotactic polypropylene than the propylene / ethylene copolymer described in Patent Document 1, but the findings of the present inventors According to, the glass transition temperature is high due to the small amount of comonomer other than propylene, which is considered to be observed near room temperature. Therefore, since the base polymer becomes brittle at a low temperature range, the stress relaxation property of the adhesive is lost, and as a result, there is a problem that it is easy to peel.
- Patent Documents 3 and 4 disclose a technique for obtaining a hot melt adhesive excellent in adhesiveness using a virtually completely amorphous soft polypropylene polymer having no heat of crystal melting.
- an amorphous soft polypropylene polymer having no crystals is used, sufficient heat resistance is not exhibited even when crystalline isotactic polypropylene is blended, and particularly at high temperatures. It is considered that sufficient performance is not exhibited in mechanical strength and creep resistance.
- Patent Document 5 discloses a technique of an adhesive composition using a propylene / 1-butene random copolymer having high stereoregularity.
- Such propylene / 1-butene random copolymers have good compatibility with crystalline isotactic polypropylene compared to the previous propylene / ethylene copolymers, but on the other hand are very rigid and hot melt bonded It is difficult to develop the flexibility of the agent.
- An object of the present invention is to provide an adhesive composition excellent in flexibility, rubber elasticity, mechanical properties (strength, elongation), heat resistance (especially mechanical properties at high temperatures, rubber elasticity), and low-temperature characteristics. .
- the present invention comprises the following [1] to [5].
- An adhesive composition (Y) comprising:
- the requirements (A1) to (A8) to be satisfied by the propylene copolymer (A) are as follows.
- (A1) Shore A hardness is in the range of 20-90.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.2 to 3.5.
- M OE represents the mole fraction of the sum of the chain of propylene and ethylene and the chain of ⁇ -olefin having 4 or more carbon atoms and ethylene with respect to all dyads
- M 2 O is the ⁇ of olefin having 4 or more carbon atoms.
- M E represents the mole fraction of ethylene
- Tg Glass transition temperature
- the requirements (B1) to (B3) to be satisfied by the crystalline isotactic polypropylene (B) are as follows.
- the isotactic pentad fraction (mmmm) is 90 to 99.8%.
- the propylene copolymer (A) further satisfies one or more requirements selected from the following (A9) and (A10).
- the soft polypropylene resin composition (X) preferably satisfies any of the following requirements (X1) to (X3), more preferably satisfies the following requirement (X1), and most preferably In addition to X1), the requirement (X2) and the requirement (X3) must be satisfied at the same time.
- (X1) Differential scanning calorimeter when measured at 23 ° C. ⁇ 2 ° C. for 72 hours or longer and then cooled to ⁇ 40 ° C. or lower and measured at a heating rate of 10 ° C./min. In the (DSC) curve, it has a melting peak Tm (AX) at 30 to 80 ° C., and further shows a melting peak Tm (BX) at 100 to 175 ° C.
- the internal haze of the 2 mmt press sheet is 0.1-30% and the total light transmittance is 75-99.9%, preferably the internal haze is 0.1-25% and the total light transmittance is 80-99. 9%.
- Adhesive composition comprising 100 parts by weight of the adhesive composition (Y) and 5 to 1000 parts by weight of a low molecular weight propylene polymer (D) having a melt viscosity of 1 to 15000 mPa ⁇ s at 190 ° C. Thing (Y2).
- An adhesive composition comprising 100 parts by weight of the adhesive composition (Y) and 5 to 150 parts by weight of a low molecular weight propylene polymer (D) having a melt viscosity of 1 to 15000 mPa ⁇ s at 190 ° C. Thing (Y2).
- the low molecular weight propylene polymer (D) is preferably an isotactic polypropylene polymer or an atactic polypropylene polymer.
- a hot-melt adhesive comprising the adhesive composition (Y) or the adhesive composition (Y2).
- a pressure-sensitive adhesive comprising the adhesive composition (Y) or the adhesive composition (Y2).
- the adhesive compositions (Y) and (Y2) of the present invention are excellent in flexibility, rubber elasticity, mechanical properties (strength, elongation), heat resistance, and low-temperature characteristics, and therefore are used as adhesives used in harsh environments. It can be suitably used. Further, the adhesive compositions (Y) and (Y2) of the present invention have a feature that the crystallization rate is slow, and they do not immediately solidify (long open time) even when they are in contact with the adherend in a heated and melted state. It can be suitably used as a hot melt adhesive.
- the adhesive compositions (Y) and (Y2) of the present invention have good transparency, they are suitable as adhesives used in applications that require design properties, and are good with polyolefins, particularly polypropylene. It is also useful as an adhesive that adheres to.
- a DSC curve of PEBR-1 (first DSC measurement method) is shown.
- a DSC curve of PEBR-2 (first DSC measurement method) is shown.
- the DSC curve (1st DSC measuring method) of the propylene ethylene copolymer (PER) used by the comparative example is shown.
- the DSC curve (first DSC measuring method) of the soft propylene resin composition (X1) used in Examples 1, 2, 5, and 6 among the soft propylene resin composition (X) according to the present invention is shown.
- the DSC curve (first DSC measurement method) of the soft propylene resin composition (X2) used in Examples 3 and 4 among the soft propylene resin composition (X) according to the present invention is shown.
- the DSC curve (1st DSC measuring method) of the soft propylene resin composition (X3) used by the comparative examples 3 and 5 among soft propylene resin compositions (X) is shown.
- the DSC curve (1st DSC measuring method) of the soft propylene resin composition (X4) used by the comparative example 4 among soft propylene resin compositions (X) is shown.
- 1 is a drawing comparing NMR charts around 15 to 17.5 ppm of a propylene copolymer (PEBR-1) according to the present invention and a soft propylene resin composition (X4). This is an example of a heat-resistant creep test sample of the adhesive composition of the present invention.
- the adhesive composition (Y) of the present invention comprises a soft polypropylene resin composition (X) in which a propylene copolymer (A) having a specific physical property parameter and a crystalline isotactic polypropylene (B) are formed in a specific ratio. (C) It consists of a tackifier. Moreover, the adhesive composition (Y2) which is another form of this invention mix
- Propylene copolymer (A) The propylene copolymer (A) used in the present invention satisfies all the following requirements (A1) to (A8).
- (A1) Shore A hardness is in the range of 20 to 90, preferably 25 to 85, more preferably 27 to 80.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1.2 to 3.5, preferably 1.4 to It is 3.0, more preferably in the range of 1.6 to 2.6.
- the isotactic triad fraction (mm) calculated by 13 C-NMR is 85 to 99.9%, preferably 87 to 99.8%.
- the B value defined by the following formula (1) is 0.8 to 1.3, preferably 0.9 to 1.2, more preferably 0.9 to 1.1.
- M OE represents the mole fraction of the sum of the chain of propylene and ethylene and the chain of ⁇ -olefin having 4 or more carbon atoms and ethylene with respect to all dyads
- M 2 O is the ⁇ of olefin having 4 or more carbon atoms.
- M E represents the mole fraction of ethylene
- A6 The amount of 2,1-bond of propylene monomer in the total propylene insertion analyzed in 13 C-NMR measurement is less than 1%, preferably 0 to 0.5%, more preferably 0 to 0.1% It is.
- Tg Glass transition temperature
- MFR Melt flow rate
- the Shore A hardness according to the requirement (A1) is obtained by subjecting a specimen obtained by heat-melting the propylene copolymer (A) at 190 to 230 ° C. and press molding at a cooling temperature of 15 to 25 ° C. to 23 ° C. ⁇ 2 It is a value obtained by storing the scale for 72 hours or more in an environment of 0 ° C. and then reading the scale immediately after contact with the pressing needle using an A-type measuring instrument (according to ASTM D-2240).
- the constituent unit amount (mol%) of each comonomer in requirement (A2) is analyzed by analysis of 13 C-NMR spectrum.
- a preferred embodiment of the ⁇ -olefin having 4 to 20 carbon atoms is 1-butene.
- the propylene copolymer (A) having a molecular weight distribution in the range specified by the requirement (A3) is preferable in that it has a low molecular weight and is less sticky. Moreover, since a polymer having such a narrow molecular weight distribution generally has a narrow composition distribution, compatibility with the crystalline isotactic polypropylene (B) is greatly improved.
- Propylene copolymer (A) having an isotactic triad fraction (mm) in the range shown in requirement (A4) does not completely lose its crystallinity even when many comonomers such as ethylene and 1-butene are copolymerized. . For this reason, excellent mechanical strength, high elongation at break, and good rubber elasticity are exhibited. Further, when the propylene copolymer (A) is partially taken into the crystal part of the crystalline isotactic polypropylene (B) described later, the physical properties, particularly heat resistance, of the soft polypropylene resin composition (X) is dramatically improved. .
- the propylene copolymer (A) has a B value in the range indicated by the requirement (A5), compatibility with the crystalline isotactic polypropylene (B) described later is further improved.
- the B value is larger than the above range, it means that each monomer (propylene, ethylene, ⁇ -olefin having 4 to 20 carbon atoms) has a molecular primary structure close to an alternating copolymer in which the monomers are alternately bonded.
- the propylene copolymer (A) is inferior in compatibility with the crystalline isotactic polypropylene (B).
- the B value is smaller than the above range, it means that each monomer has a molecular primary structure close to a dense block copolymer. In this case, too, the propylene copolymer (A) and the crystalline isotactic polypropylene (B) The compatibility of is inferior.
- the propylene copolymer (A) in which the 2,1-bond amount (inversion) of the propylene monomer in the entire propylene insertion is in the range of the requirement (A6) is excellent in regioregularity. That is, since there are few 2,1-bonds which inhibit the crystallinity of the propylene copolymer (A), the propylene copolymer (A) having such physical properties is a preferred embodiment of the present invention as well as the requirement (A4).
- the 2,1-bond amount of the propylene monomer during the total propylene insertion is calculated according to the method described in JP-A-7-145212, but no peak is observed in the range of 15.0 to 17.5 ppm. Is particularly preferred.
- the propylene copolymer (A) according to the present invention has a glass transition temperature in the range indicated by the requirement (A7).
- the glass transition temperature of the propylene copolymer (A) is within this range, the adhesive composition (Y) of the present invention can be provided with practically sufficient low-temperature characteristics.
- the MFR range of the propylene copolymer (A) is within the range of the requirement (A8), both physical properties (mechanical properties, heat resistance, etc.) and processability of the adhesive composition can be achieved.
- the MFR value of the propylene copolymer (A) is in a relatively low region as compared with the conventional APAO and the like, but this imparts sufficient heat resistance to the adhesive composition (Y) of the present invention. It is.
- improvement of workability can be realized by an adhesive composition (Y2) obtained by blending a specific low molecular weight propylene polymer (D) with the adhesive composition (Y), and details thereof will be described later. .
- the propylene copolymer (A) of the present invention preferably satisfies one or more selected from the following requirements (A9) and (A10) in addition to the above requirements (A1) to (A8).
- the storage elastic modulus at 23 ° C. to 40 ° C. is in the range of 1 MPa to 100 MPa, preferably 1 to 50 MPa, more preferably 1 to 20 MPa.
- the one having the maximum peak is defined as Tm (A) 1 .
- the measurement is performed on a specimen immediately after the condition adjustment for 23 hours or more at 23 ° C. ⁇ 2 ° C. It should be noted that the test specimen at this time was prepared under the press molding conditions described in the requirement (A1), and was not heat-treated at a specific temperature before the condition adjustment.
- the fact that the propylene copolymer (A) satisfies the requirement (A9) means that the propylene copolymer (A) forms a fine crystal component.
- the propylene copolymer (A) is likely to be partly incorporated into the crystalline part of the crystalline isotactic polypropylene (B), and the mechanical properties of the adhesive composition (Y), rubber Elasticity and heat resistance are dramatically improved.
- Tm (A) 1 and Tm (A) 2 are shown in FIGS.
- the melting enthalpies ⁇ H (A) 1 and H (A) 2 are determined by the method described in JIS K7122.
- the propylene copolymer (A) does not show the melting peak Tm (A) 1 defined in the requirement (A9), it can be suitably used in the present invention as long as the requirement (A10) is satisfied.
- the propylene copolymer (A) satisfies the requirement (A10), it means that the propylene copolymer (A) forms a fine crystalline component. Since such fine crystal components are completely melted when the temperature exceeds at least 80 ° C., the storage elastic modulus at 23 ° C. to 40 ° C. is in the range of 1 MPa to 100 MPa, preferably 1 to 50 MPa, more preferably 1 to 20 MPa.
- the storage elastic modulus E ′ is less than 1 MPa in the range of 30 to 80 ° C., preferably 35 to 70 ° C., more preferably 40 to 70 ° C.
- the solid viscoelasticity measurement of this invention is observed on tension mode and 1 Hz conditions. The case where both the requirement (A9) and the requirement (A10) are satisfied is particularly suitable in the present invention.
- the propylene copolymer (A) of the present invention is usually obtained by copolymerizing propylene, ethylene and an ⁇ -olefin having 4 to 20 carbon atoms in the presence of a metallocene catalyst.
- a metallocene catalyst for example, the catalyst of International Publication No. 2004-087775, for example, the catalysts described in Examples e1 to e5 can be used without limitation.
- Crystalline isotactic polypropylene (B) The crystalline isotactic polypropylene (B) used in the present invention satisfies all the following requirements (B1) to (B3).
- the melting point Tm (B) observed by DSC measurement obtained when measured at 10 ° C./min is 100 to 175 ° C., preferably 110 to 170 ° C., more preferably 125 to 170 ° C.
- the isotactic pentad fraction (mmmm) is 90% to 99.8%, preferably 93% to 99.7%, more preferably 95% to 99.6%.
- Melt flow rate (MFR) (ASTMD 1238, 230 ° C., under 2.16 kg load) is 0.1 to 100 g / 10 min, preferably 1.0 to 60 g / 10 min, more preferably 1.5 to 50 g / 10 min. It is.
- the melting point Tm (B) of requirement (B1) is maintained at 200 ° C. for 10 minutes in a differential scanning calorimeter (DSC) measuring device, then cooled to ⁇ 20 ° C. at a temperature drop rate of 10 ° C./min, and 1 at ⁇ 20 ° C. It is determined by the DSC measurement obtained when the temperature is kept again for 10 minutes and then measured again at a heating rate of 10 ° C./min.
- DSC differential scanning calorimeter
- this DSC measurement method may be referred to as “second DSC measurement method and DSC curve creation method according to the present invention”.
- the isotactic pentad fraction (mmmm) in requirement (B2) indicates the abundance ratio of isotactic chains in pentad units in the molecular chain measured using 13 C-NMR. This is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded.
- the isotactic pentad fraction (mmmm fraction) can be obtained by the method described in, for example, Japanese Patent Application Laid-Open No. 2007-186664.
- the crystalline isotactic polypropylene (B) satisfies all the requirements (B1) to (B3), it contributes to improvement of mechanical properties and heat resistance of the soft polypropylene resin composition (X), and the propylene copolymer (A) Good compatibility with.
- the crystalline isotactic polypropylene (B) of the present invention is propylene / ⁇ -olefin having 2 to 20 carbon atoms (provided that it satisfies the requirements (B1) to (B3)).
- the copolymer may be a random copolymer (except propylene) or a propylene block copolymer, but is preferably a homopolypropylene or a propylene- ⁇ -olefin random copolymer having 2 to 20 carbon atoms.
- homopolypropylene is particularly preferable, and from the viewpoint of excellent flexibility and transparency, the obtained composition is particularly propylene / alpha-olefin random copolymer having 2 to 20 carbon atoms. Polymers are preferred.
- examples of the ⁇ -olefin having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, copolymers with ethylene, ⁇ -olefins having 4 to 10 carbon atoms Or a copolymer of ethylene and an ⁇ -olefin having 4 to 10 carbon atoms.
- the structural unit derived from propylene contains 90 mol% or more with respect to a total of 100 mol% of the structural unit derived from propylene and the structural unit derived from ⁇ -olefin having 2 to 20 carbon atoms other than propylene.
- the crystalline isotactic polypropylene (B) used in the present invention has a heat of fusion ⁇ H (B) corresponding to the melting point Tm (B) specified in the requirement (B1) of 50 to 130 J / g, preferably 55 to 120 J. / G is preferred.
- the heat of fusion ⁇ H (B) of the crystalline isotactic polypropylene (B) is within this range, the soft polypropylene polymer composition and the polypropylene polymer composition having excellent moldability, heat resistance and transparency and little stickiness This is preferable because a product is obtained.
- the tensile elastic modulus of the crystalline isotactic polypropylene (B) in the present invention is preferably 500 to 3000 MPa, preferably 600 to 2500 MPa, more preferably 650 to 2200 MPa.
- the tensile modulus is a value obtained by measuring a 2 mm thick press sheet at 23 ° C. in accordance with JIS K7113-2.
- the crystalline isotactic polypropylene (B) used in the present invention can be produced by various methods, for example, using a stereoregular catalyst.
- titanium trichloride or a titanium trichloride composition is a solid titanium catalyst component supported on a carrier having a specific surface area of 100 m 2 / g or more, or magnesium, halogen, electron Examples include a solid titanium catalyst component supported on a carrier having a donor (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium as essential components, and these essential components having a specific surface area of 100 m 2 / g or more. .
- the organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, and the like.
- the organoaluminum compound can be appropriately selected according to the type of titanium catalyst component used.
- an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, or a boron atom can be used, and preferably, an ester compound and an ether compound having the above atoms are used. .
- Such a catalyst may be further activated by a technique such as co-grinding, or an olefin as described above may be prepolymerized.
- the crystalline isotactic polypropylene (B) in the present invention can also be produced with a known metallocene catalyst.
- Soft polypropylene resin composition (X) The soft polypropylene resin composition (X) of the present invention is a composition composed of the propylene copolymer (A) and the crystalline isotactic polypropylene (B).
- the soft polypropylene resin composition (X) comprises 40 to 98% by weight of the propylene copolymer (A), preferably 60 to 97% by weight, more preferably 70 to 95% by weight, and 2% of crystalline isotactic polypropylene (B). -60% by weight, preferably 3-40% by weight, more preferably 5-30% by weight (provided that the total of component (A) and component (B) is 100% by weight).
- the method for obtaining the soft polypropylene resin composition (X) used in the present invention is not particularly limited, but the composition is obtained by polymerizing the propylene copolymer (A) and the crystalline isotactic polypropylene (B) simultaneously or sequentially.
- Method a method obtained by mixing independently obtained propylene copolymer (A) and crystalline isotactic polypropylene (B), and further, either propylene copolymer (A) or crystalline isotactic polypropylene (B) is mixed first. There is a method in which the first manufactured in the process of manufacturing and producing the other one is added.
- the soft polypropylene resin composition (X) of the present invention may contain other polymers as optional components within the range not impairing the object of the present invention.
- the blending amount is not particularly limited, but for example, it is preferably about 0.1 to 30 parts by weight with respect to 100 parts by weight of the soft polypropylene resin composition (X) of the present invention.
- the soft polypropylene resin composition (X) Improved flexibility and low temperature characteristics.
- the polymer component is composed only of the propylene copolymer (A) and the crystalline isotactic polypropylene (B) without including other resins.
- the transparency is particularly excellent.
- the soft polypropylene resin composition (X) of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a nucleus within a range not impairing the object of the present invention.
- Additives such as agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors may be blended as necessary.
- the soft polypropylene resin composition (X) of the present invention may be graft-modified with a polar monomer or the like. Specifically, it means a form in which at least one or both of the propylene copolymer (A) and the crystalline isotactic polypropylene (B) constituting the soft polypropylene resin composition (X) are graft-modified with a polar monomer.
- soft polypropylene resin composition (X) of the present invention those having physical properties satisfying the following requirements (X1) and (X2) are particularly suitable.
- the soft polypropylene resin composition (X) having such Tm (AX) means that the propylene copolymer (A) in the soft polypropylene resin composition (X) forms a fine crystal component. .
- the propylene copolymer (A) is likely to be partly incorporated into the crystalline part of the crystalline isotactic polypropylene (B), and the mechanical properties of the adhesive composition (Y), rubber Elasticity and heat resistance are dramatically improved.
- transition heat (melting enthalpy) ⁇ H (AX) giving the melting peak Tm (AX) is 0.5 to 20 J / g, preferably 0.5 to 15 J / g, more preferably 0.5 to 12 J / g
- transition heat (melting enthalpy) ⁇ H (BX) giving a melting peak Tm (BX) is 3 to 80 J / g, preferably 5 to 70 J / g g, more preferably in the range of 10-60 J / g.
- the hardness of the soft polypropylene resin composition (X) of the present invention is not particularly limited as long as it satisfies the requirements (X1) and (X2), but the Shore A hardness is 40 to 95, preferably 55 to 93, More preferably, it is in the range of 65 to 90.
- the Shore A hardness at this time is determined by the specimen and method prepared under the same conditions as those for measuring the hardness of the propylene copolymer (A) in the requirement (A1) described above.
- the soft polypropylene resin composition (X) of the present invention include those satisfying the following requirement (X3) in addition to the requirements (X1) and (X2). (X3) of 2 mmt press sheet
- the internal haze is 0.1 to 30% and the total light transmittance is 75 to 99.9%, preferably the internal haze is 0.1 to 25% and the total light transmittance is 80 to 99.9%.
- the internal haze and total light transmittance are determined by the following method: A test specimen having a thickness of 2 mm obtained by heat-melting at 190 to 230 ° C. and press molding at a cooling temperature of 15 to 25 ° C. Measures diffused and transmitted light in a cyclohexanol solution using a digital turbidimeter “NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd., and a C light source. Calculate
- the soft polypropylene resin composition (X) according to the present invention is characterized in that the phase separation structure of the propylene copolymer (A) and the crystalline isotactic polypropylene (B) is not observed.
- this phase separation structure was dye
- the melt flow rate (MFR) (ASTM D1238, 230 ° C., under a load of 2.16 kg) of the soft polypropylene resin composition (X) according to the present invention is the same as that of the propylene copolymer (A) and crystalline isotactic polypropylene (B ) Depending on the MFR. Usually, it is in the range of 0.5 to 500 g / 10 min, preferably 1 to 50 g / 10 min, more preferably 2 to 12 g / 10 min.
- Tackifier (C) examples include natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenol resin, xylene resin, styrene resin, and low molecular weight styrene resin. Examples thereof include at least one resin selected from a resin and an isoprene-based resin.
- rosin resins polyterpene resins, and synthetic petroleum resins are preferable, and those having an aliphatic and / or alicyclic structure are more preferable.
- Particularly preferred as petroleum resins having an aliphatic and / or alicyclic structure are partially and fully hydrogenated rosins and their derivatives for rosin resins, and homopolymers or copolymers of cyclic terpenes for polyterpene resins.
- Examples of coal and synthetic petroleum resins include aliphatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, and hydrogenated products of copolymers of naphtha cracked oil and various terpenes.
- those having a softening point in the range of 25 to 160 ° C. are preferred. If the softening point is less than 25 ° C., the surface may bleed. Conversely, if the softening point exceeds 160 ° C., the viscosity during melting is high. The workability becomes poor.
- there are Alcon P-70, Archon P-90, Archon P-100, Archon P-115, Archon P-125, Archon P-140 (all of which are trade names) manufactured by Arakawa Chemical Industries, Ltd. Preferably used.
- tackifiers (C) can be used alone or in admixture of two or more.
- Adhesive composition (Y) and adhesive composition (Y2) The adhesive composition (Y) of the present invention comprises 10 to 70 parts by weight, preferably 15 to 65 parts by weight, more preferably 25 to 60 parts by weight of the soft polypropylene resin composition (X), and the tackifier ( C) 30 to 90 parts by weight, preferably 35 to 85 parts by weight, more preferably 40 to 75 parts by weight (here, the total amount of component (X) and component (C) is 100 parts by weight).
- the adhesive composition (Y) By forming the adhesive composition (Y) with such a composition, various physical properties such as flexibility, mechanical properties, heat resistance, and adhesive properties can be balanced.
- a composition in which the soft polypropylene resin composition (X) is larger than the tackifier (C) is preferable.
- the soft polypropylene resin composition (X) preferably 55 to 65 parts by weight and 30 to 49 parts by weight of the tackifier (C), preferably 35 to 45 parts by weight are preferred.
- the flow modifier examples include paraffinic process oil, polyolefin wax, low molecular weight polyolefin, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, epoxy polymer plasticizer, naphthenic oil, etc. Any known one can be used as long as it lowers the melt viscosity of the adhesive composition (Y). Among them, polyolefin waxes and low molecular weight polyolefins are preferable, and the melt viscosity at 190 ° C. is preferably 1 to 15000 mPa ⁇ s.
- a low molecular weight propylene polymer (D) having a molecular weight of preferably 10 to 12000 mPa ⁇ s, more preferably 25 to 10000 mPa ⁇ s can be suitably used.
- Such a low molecular weight propylene polymer (D) is a polymer comprising propylene-derived constitutional units in an amount of 40 to 100 mol%, preferably 60 to 100 mol%, particularly preferably 75 to 100 mol%.
- Wax high wax manufactured by Mitsui Chemicals, Inc.
- amorphous polypropylene, etc. and those having excellent compatibility with the soft polypropylene resin composition (X) in the adhesive composition (Y2) should be used.
- the fluidity can be improved without impairing the mechanical properties, heat resistance, and transparency.
- the stereoregularity of the low-molecular-weight propylene polymer (D) is not particularly limited, but is an atactic polypropylene-based polymer or isotactic in that the compatibility with the soft polypropylene resin composition (X) is further improved.
- a tech polypropylene polymer is preferred.
- the amorphous polypropylene is not particularly limited, but preferably has a melting peak Tm of 75 to 160 ° C., more preferably 100 to 155 ° C., and further provides a melting peak Tm from the viewpoint of heat resistance.
- the heat (melting enthalpy) ⁇ H is 5 to 60 J / g, more preferably 15 to 45 J / g. Hold at 200 ° C. for 10 minutes in the DSC measuring device, cool to ⁇ 20 ° C. at a temperature drop rate of 20 ° C./min, hold at ⁇ 20 ° C. for 1 minute, and then heat again to 200 ° C. at a temperature increase rate of 20 ° C./min. Thus, a DSC curve was created.
- An adhesive composition (Y2) according to another embodiment of the present invention using such a low molecular weight propylene polymer (D) is added to 100 parts by weight of the adhesive composition (Y) with the low molecular weight propylene polymer.
- the blend (D) is blended in an amount of 5 to 1000 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight.
- These flow modifiers may be used alone or in admixture of two or more.
- the adhesive composition (Y) of the present invention includes the soft polypropylene resin composition (X) and a tackifier (C), and various additives such as inorganic fillers, antioxidants, and weathering stabilizers used as necessary. It is obtained by melt mixing the agent.
- the adhesive composition (Y2) of the present invention includes the soft polypropylene resin composition (X), a tackifier (C), a low molecular weight propylene polymer (D), and an inorganic filler used as necessary. It can be obtained by melt-mixing various additives such as antioxidants and weathering stabilizers.
- the method of melt mixing is not particularly limited, and examples thereof include known mixing methods such as an extruder, an open roll mill, a Banbury mixer, a kneader, and a melt mixing tank.
- the melt mixing temperature is usually from 100 to 250 ° C., preferably from 160 to 230 ° C.
- the adhesive composition (Y) or the adhesive composition (Y2) of the present invention has an appropriate setting time, the open time can be adjusted to be long. Therefore, the adhesive composition (Y) or the adhesive composition (Y2) of the present invention can be suitably used as a hot-melt adhesive or a pressure-sensitive adhesive, and among them, it can be suitably used as a hot-melt adhesive.
- the adhesive composition (Y) or the adhesive composition (Y2) of the present invention is an adhesive for bonding various adherends such as plastic, glass, metal, fiber, artificial / natural leather, paper, and wood.
- adherends such as plastic, glass, metal, fiber, artificial / natural leather, paper, and wood.
- at least one adherend is a plastic material, and among them, a polyolefin material, particularly preferably a polypropylene material is preferable.
- each component constituting the adhesive composition used in the examples (a component corresponding to the propylene copolymer (A) of the present invention, a component corresponding to the crystalline isotactic polypropylene (B) of the present invention, the present invention)
- the component corresponding to the soft polypropylene resin composition (X)) and each component constituting the adhesive composition used in the comparative example will be described.
- composition (1-1) Propylene / ethylene / 1-butene copolymer corresponding to propylene copolymer (A) according to the present invention
- a polymerization catalyst / co-catalyst JP-A-2007-186664 Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride / methylaluminoxane (manufactured by Tosoh Finechem,
- the following two types of propylene / ethylene / 1-butene copolymers are obtained by polymerizing ethylene, propylene and 1-butene as raw materials in a hexane solution using a continuous polymerization facility.
- PEBR-1 and PEBR-2 were obtained.
- Table 1 shows the physical properties of PEBR-1 and PEBR-2.
- DSC curves first DSC measurement method
- a 100 ⁇ m PET film manufactured by Toray, Lumirror was used as a release film during press molding.
- the separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL.
- the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C, and the mobile phase is Using o-dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, it was moved at 1.0 ml / min, the sample concentration was 15 mg / 10 ml, and the sample injection volume was 500 A microliter was used, and a differential refractometer was used as a detector.
- the standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw ⁇ 1000 and Mw> 4 ⁇ 106, and that of Pressure Chemical Co. was used for 1000 ⁇ Mw ⁇ 4 ⁇ 106.
- MFR Melt flow rate
- the propylene copolymer (A) according to the present invention was measured by the “second DSC measurement method and DSC curve creation method according to the present invention” used for determining the melting point of the crystalline isotactic polypropylene (B) described later. In such a case, the melting point may not be observed, but such a propylene copolymer (A) is also preferably used in the present invention.
- MFR Melt flow rate
- the soft polypropylene resin composition (X1) was used in Examples 1 and 2 and Examples 5 and 6 described later.
- Soft polypropylene resin composition (X-2) comprising propylene / ethylene / 1-butene copolymer (PEBR-2) and isotactic polypropylene (PP) 90% by weight of the propylene / ethylene / 1-butene copolymer (PEBR-2) and 10% by weight of isotactic polypropylene (PP) were kneaded (190 ° C., 3 minutes, 40 rpm) with a lab plast mill (manufactured by Toyo Seiki). Thus, a soft polypropylene resin composition (X2) was obtained.
- Table 2 shows the physical properties of the soft polypropylene resin composition (X2). Further, the DSC curve (first DSC measurement method) is shown in FIG.
- the soft polypropylene resin composition (X2) was used in Examples 3 and 4 described later.
- Soft polypropylene resin composition (X-3) comprising propylene / ethylene copolymer (PER) and isotactic polypropylene (PP)
- the propylene / ethylene copolymer (PER) 85 wt% and isotactic polypropylene (PP) 15 wt% are kneaded (190 ° C., 3 min, 40 rpm) with a Laboplast mill (manufactured by Toyo Seiki), and a soft polypropylene resin composition A product (X3) was obtained.
- Table 2 shows the physical properties of the soft polypropylene resin composition (X3).
- a DSC curve first DSC measurement method
- the soft polypropylene resin composition (X3) was used in Comparative Examples 3 and 5 described later.
- the soft polypropylene resin composition (X4) has a melting point near 130 ° C., it contains a crystalline polypropylene component corresponding to the isotactic polypropylene (PP) in the soft polypropylene resin compositions (X1) to (X3).
- FIG. 8 shows the NMR measurement results (around 15.0 to 17.5 ppm) compared with the previous propylene / ethylene / 1-butene copolymer (PEBR-1).
- FIG. 8 shows that the soft polypropylene resin composition (X4) has a large peak in the vicinity of 15.0 to 17.5 ppm, and thus the soft polypropylene resin composition (X4) can be said to be a material with low positional regularity.
- Melting points Tm (AX) and Tm (BX) and melting enthalpies ⁇ H (AX) and ⁇ H (BX) are described above as “First DSC measurement method and DSC curve creation method according to the present invention”. Based on the analysis. In addition, using a measuring device manufactured by Perkin Elmer, the test specimen was a 3 mm thick press sheet prepared under the same conditions as those used for Shore A hardness measurement, and the condition was adjusted at 23 ° C. ⁇ 2 ° C. for 2 weeks before the test. What was performed was used.
- MFR Melt flow rate
- the scale was read immediately after contact with the pressing needle using an A-type measuring instrument (according to ASTM D-2240). For those having a Shore A hardness of more than 90, the scale after 5 illnesses after contact with the pressing needle was read using a D-type measuring instrument (according to ASTM D-2240).
- a 50 ⁇ m release PET film (made by Toray Film Processing Co., Ltd.) with a silicon treatment on the surface was used as a release film.
- a 50 ⁇ m release PET film (made by Toray Film Processing Co., Ltd.) with a silicon treatment on the surface was used as a release film.
- Residual strain (%) 100 ⁇ (thickness before test ⁇ thickness after test) / (thickness before test ⁇ thickness at compression) It means that it has rubber elasticity, so that this residual strain value is low.
- a 50 ⁇ m release PET film (made by Toray Film Processing Co., Ltd.) with a silicon treatment on the surface was used as a release film.
- a 50 ⁇ m release PET film (made by Toray Film Processing Co., Ltd.) with a silicon treatment on the surface was used as a release film.
- This adhesion test sample was put into an oven set at 80 ° C., and a load was applied to 120 g / cm 2 in a state where one side was fixed and suspended, and held for 30 minutes to stabilize.
- the set temperature of the oven was 180 ° C., and the temperature at which the sample dropped was observed while gradually raising the temperature inside the oven, and this was taken as the drop temperature. Moreover, 80 degreeC was made into the fall temperature for what fell, when hold
- a 50 ⁇ m release PET film (made by Toray Film Processing Co., Ltd.) with a silicon treatment on the surface was used as a release film.
- This press sheet was measured for diffuse transmitted light amount and total transmitted light amount in air using a digital turbidimeter “NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd., C light source. The light transmittance was calculated.
- Total haze 100 ⁇ (diffuse transmitted light amount) / (total transmitted light amount)
- Total light transmittance 100 ⁇ (total transmitted light amount) / (incident light amount) [Solidification speed (crystallization speed)]
- the solidification rate was evaluated based on the crystallization temperature Tc observed in DSC measurement.
- the crystallization temperature Tc at this time is analyzed based on the following “third DSC measurement method and DSC curve creation method relating to the present invention”, and is cooled from 200 ° C. to ⁇ 20 ° C. at a temperature decrease rate of 20 ° C./min.
- the maximum exothermic peak observed between them was defined as Tc.
- “Third DSC measurement method and DSC curve creation method according to the present invention” Hold at 200 ° C. for 10 minutes in the DSC measuring device, cool to ⁇ 20 ° C. at a temperature drop rate of 20 ° C./min, hold at ⁇ 20 ° C. for 1 minute, and then heat again to 200 ° C. at a temperature increase rate of 20 ° C./min. Thus, a DSC curve was created.
- Example 1 Laboplast mill (Toyo Seiki) 60 parts by weight of a soft polypropylene resin composition (X1) and 40 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, trade name: Alcon P-125, manufactured by Arakawa Chemical) Manufactured) and kneaded (190 ° C., 5 min, 60 rpm) to obtain an adhesive composition (Y) -1.
- a tackifier alicyclic saturated hydrocarbon resin, trade name: Alcon P-125, manufactured by Arakawa Chemical
- Table 3 shows the evaluation results of the adhesive composition (Y) -1.
- Example 2 40 parts by weight of a soft polypropylene resin composition (X1) and 60 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, trade name: Alcon P-125, manufactured by Arakawa Chemical Co., Ltd.) Manufactured) and kneaded (190 ° C., 5 min, 60 rpm) to obtain an adhesive composition (Y) -2.
- Table 3 shows the evaluation results of the adhesive composition (Y) -2.
- Example 3 60 parts by weight of a soft polypropylene resin composition (X2) and 40 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, trade name: Alcon P-125, manufactured by Arakawa Chemical Co., Ltd.) Kneading (190 ° C., 5 min, 60 rpm) to obtain an adhesive composition (Y) -3.
- Table 3 shows the evaluation results of the adhesive composition (Y) -3.
- Example 4 40 parts by weight of a soft polypropylene resin composition (X2) and 60 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, manufactured by Arakawa Chemical Co., Ltd .: Alcon P-125) were added to a lab plast mill (Toyo Seiki). Manufactured) and kneaded (190 ° C., 5 min, 60 rpm) to obtain an adhesive composition (Y) -4. Table 3 shows the evaluation results of the adhesive composition (Y) -4.
- a tackifier C
- alicyclic saturated hydrocarbon resin manufactured by Arakawa Chemical Co., Ltd .: Alcon P-125
- Table 3 shows the evaluation results of the adhesive composition (Y) -4.
- Example 5 60 parts by weight of a soft polypropylene resin composition (X1), 40 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, manufactured by Arakawa Chemical Co., Ltd .: Alcon P-125), (X1) and (C ) With a low molecular weight propylene polymer (D1) blended with 30 parts by weight of polypropylene wax (Mitsui Chemicals, brand name: NP055, melt viscosity at 190 ° C. 52 mPa ⁇ s) The mixture was kneaded (190 ° C., 5 min, 60 rpm) with a plast mill (manufactured by Toyo Seiki) to obtain an adhesive composition (Y2) -1. Table 4 shows the evaluation results of the adhesive composition (Y2) -1. The melt viscosity of polypropylene wax was measured at 190 ° C. using a Brookfield viscometer.
- C alicyclic saturated hydrocarbon resin, manufactured by Arakawa Chemical Co.
- Example 6 60 parts by weight of a soft polypropylene resin composition (X1), 40 parts by weight of a tackifier (C) (alicyclic saturated hydrocarbon resin, manufactured by Arakawa Chemical Co., Ltd .: Alcon P-125), (X1) and (C Laboplast mill is prepared by blending 30 parts by weight of APAO (manufactured by Huntsman, brand name: RT2180, melt viscosity at 190 ° C., 8000 mPa ⁇ s) as a low molecular weight propylene polymer (D2) Kneading (manufactured by Toyo Seiki) (190 ° C., 5 min, 60 rpm) to obtain an adhesive composition (Y2) -2.
- Table 4 shows the evaluation results of the adhesive composition (Y2) -1.
- the melt viscosity of APAO was measured at 190 ° C. using a Brookfield viscometer.
- the adhesive composition (Y) of the present invention has good flexibility and rubber elasticity, and has good stress / deformability followability.
- the adhesive composition (Y) of the present invention is flexible but also has good strength and adhesive performance at high temperatures and excellent heat resistance.
- the adhesive composition (Y) of the present invention has good transparency.
- the adhesive composition of this invention has moderate solidification time, and can adjust the open time of a hot-melt-adhesive long.
- MFR Melt flow rate
- the upper and lower ends of the test piece were lightly fixed with a chuck jig so that the upper and lower ends of the test piece were 20 mm at room temperature, and fixed firmly after cooling to ⁇ 40 ° C. After the temperature was raised to 100 ° C. and the temperature was stabilized, a tension of 0.1 MPa was applied, and the creep amount (%) after 30 minutes was measured.
- a 100 ⁇ m PET film manufactured by Toray, Lumirror was used as a release film during press molding.
- compositions (Z) -1 and (Z) -2 were compared with the soft polypropylene resin composition (X1), and increased in melt flow rate and heat-resistant creep amount. Decrease is observed. This means an improvement in fluidity and heat resistance.
- compositions (Z) -3 and (Z) -4 are more fluid and heat resistant than the soft polypropylene resin composition (X2). An improvement is observed.
Abstract
Description
(A6)13C-NMR測定において解析される、全プロピレン挿入中のプロピレンモノマーの2,1-結合量が1%未満である。
本発明で用いられるプロピレンコポリマー(A)は、下記要件(A1)~(A8)を全て満たすものである。
(A6)13C-NMR測定において解析される、全プロピレン挿入中のプロピレンモノマーの2,1-結合量が1%未満、好ましくは0~0.5%、より好ましくは0~0.1%である。
本発明で用いられる結晶性アイソタクティックポリプロピレン(B)は以下の要件(B1)~(B3)を全て満たすものである。
また、要件(B2)におけるアイソタクティックペンタッド分率(mmmm)は、13C-NMRを使用して測定される分子鎖中のペンタッド単位でのアイソタクチック連鎖の存在割合を示しており、プロピレンモノマー単位が5個連続してメソ結合した連鎖の中心にあるプロピレンモノマー単位の分率である。
本発明の軟質ポリプロピレン樹脂組成物(X)は、前記プロピレンコポリマー(A)と結晶性アイソタクティックポリプロピレン(B)とから構成される組成物である。
(X3)2mmtプレスシートの内部ヘイズが0.1~30%かつ全光線透過率が75~99.9%、好ましくは内部ヘイズが0.1~25%、全光線透過率が80~99.9%である。なお、内部ヘイズおよび全光線透過率は以下の方法で決定される;190~230℃で加熱溶融させた後15~25℃の冷却温度でプレス成形して得られた2mm厚みの試験体を、日本電色工業(株)製のデジタル濁度計「NDH-2000」、C光源を用いてシクロヘキサノール溶液中で拡散透過光量および全透過光量を測定し、下式により内部ヘイズ、全光線透過率を計算する。
全光線透過率=100×(全透過光量)/(入射光量)
本発明に係る軟質ポリプロピレン樹脂組成物(X)は、前記プロピレンコポリマー(A)と結晶性アイソタクティックポリプロピレン(B)の相分離構造が観察されないことが特長である。
本発明で用いられる粘着付与剤(C)としては、例えば、天然ロジン、変性ロジン、ポリテルペン系樹脂、合成石油樹脂、クマロン系樹脂、フェノール系樹脂、キシレン系樹脂、スチレン系樹脂、低分子量スチレン系樹脂、およびイソプレン系樹脂から選ばれる少なくとも1種の樹脂を挙げることができる。
本発明の接着剤組成物(Y)は、前記軟質ポリプロピレン樹脂組成物(X)10~70重量部、好ましくは15~65重量部、より好ましくは25~60重量部と、前記粘着付与剤(C)30~90重量部、好ましくは35~85重量部、より好ましくは40~75重量部(ここで成分(X)と成分(C)の合計量を100重量部とする)からなる。
(1-1)本発明に係るプロピレンコポリマー(A)に対応するプロピレン・エチレン・1-ブテン共重合体
重合用触媒/助触媒として、特開2007-186664号公報に記載の方法で調製したジフェニルメチレン(3-tert-ブチル-5-エチルシクロペンタジエニル)(2,7-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド/メチルアルミノキサン(東ソー・ファインケム社製、アルミニウム換算で0.3mmol)と、原料となるエチレン、プロピレン、1-ブテンを、連続重合設備を用いてヘキサン溶液中で重合することで以下の2種類のプロピレン・エチレン・1-ブテン共重合体(PEBR-1)、(PEBR-2)を得た。これらのPEBR-1、PEBR-2の物性を表1に示す。また、DSCカーブ(第一のDSC測定法)を各々、図1および図2に示す。
エクソンモービル社製 VISTAMAXX(銘柄名 VM6100)を使用した。このPERの物性を表1に示す。また、DSCカーブ(第一のDSC測定法)を図3に示す。
国際公開第2004/087775号パンフレットに記載のメタロセン触媒を用いてプロピレン・1-ブテン共重合体(PBR)を得た。このPBRの物性を表1に示す。
190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して3mm厚みのプレスシートを作成した。これを23℃±2℃の環境下で72時間保管して後、A型測定器を用い、押針接触後直ちに目盛りを読み取った(ASTM D-2240に準拠)。
13C-NMRスペクトルの解析により求めた。
GPC(ゲルパーミエーションクロマトグラフィー)を用い、オルトジクロロベンゼン溶媒(移動相)とし、カラム温度140℃で測定した(ポリスチレン換算、Mw:重量平均分子量、Mn:数平均分子量)。具体的には分子量分布(Mw/Mn)は、Waters社製ゲル浸透クロマトグラフAlliance GPC- 2000型を用い、以下のようにして測定した。分離カラムは、TSKgel GNH6-HTを2本、およびTSKgel GNH6-HTLを2本であり、カラムサイズはいずれも直径7.5 mm、長さ300 mmであり、カラム温度は140 ℃とし、移動相にはo-ジクロロベンゼン(和光純薬工業)および酸化防止剤としてBHT(武田薬品)0.025重量%を用いて、1.0 ml/分で移動させ、試料濃度は15 mg/10 mlとし、試料注入量は500マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンは、分子量がMw <1000、およびMw >4×106については東ソー社製を用いて、1000 ≦ Mw ≦4×106についてはプレッシャーケミカル社製を用いた。
13C-NMRスペクトルの解析により求めた。
特開2007-186664号公報に記載された方法に従って、13C-NMRスペクトルの解析により求めた。
13C-NMRスペクトルの解析により求めた。
パーキンエルマー社製の測定装置を用い、本発明に関する第1のDSC測定方法およびDSC曲線作成方法で得られた吸熱曲線を解析して求めた。
ASTMD1238に準拠し、230℃、2.16kg荷重下で測定した。
融点および融解エンタルピーは、以下の『本発明に関する第1のDSC測定方法およびDSC曲線作成方法』に基づいて解析した。なおパーキンエルマー社製の測定装置を用い、試験体は、ショアーA硬度測定に用いたものと同一の条件で作成した3mm厚みのプレスシートを試験前に23℃±2℃で2週間の状態調節を行ったものを用いた。
23℃±2℃で72時間以上の状態調節を実施した後の試験体にて、-40℃まで冷却してから昇温速度10℃/minで測定したときに得られるDSC曲線を作成した。このときに得られた融点をTm(A)1、融解エンタルピーをΔH(A)1とした。
Rheometrics社製のRSA-II型試験機にて、引張りモード、測定周波数1Hz、昇温速度3℃/min、測定温度は-40~100℃(または測定限界温度)の範囲で測定し、E’の温度依存性を示す曲線を得た。この曲線を解析して、23℃、40℃におけるE’(MPa)および、E’が1MPa未満になる温度を解析した。なお、試験体は、ショアーA硬度測定に用いたものと同一の条件で作成した500μm厚みのプレスシートを用いた、試験前に23℃±2℃で72時間の状態調節を行った。
(2-1)本発明の結晶性アイソタクティックポリプロピレン(B)に対応するアイソタクティックポリプロピレン(PP)
Tm=160.4℃、ΔH=99.6J/g、MFR(230℃、2.16kg荷重)=3.0g/10min、mmmm=97.9%
上記アイソタクティックポリプロピレン(PP)の物性値は、以下の方法で測定した。
融点Tm(B)および融解エンタルピーΔH(B)は、以下の『本発明に関する第2のDSC測定方法およびDSC曲線作成方法』に基づいて解析した。なおパーキンエルマー社製の測定装置を用いた。
DSC測定装置内で10分間200℃保持した後、降温速度10℃/minで-20℃まで冷却し、-20℃で1分間保持した後、再度昇温速度10℃/minで測定したときに得られるDSC曲線を作成した。
13C-NMRスペクトルの解析により求めた。
プロピレンコポリマー(A)のMFR測定法(既述)と同一方法を採用した。
(3-1)プロピレン・エチレン・1-ブテン共重合体(PEBR-1)とアイソタクティックポリプロピレン(PP)からなる軟質ポリプロピレン樹脂組成物(X-1)
前記のプロピレン・エチレン・1-ブテン共重合体(PEBR-1)85wt%、アイソタクティックポリプロピレン(PP)15wt%を、ラボプラストミル(東洋精機製)にて混練(190℃、3min、40rpm)し、軟質ポリプロピレン樹脂組成物(X1)を得た。軟質ポリプロピレン樹脂組成物(X1)の物性を表2に示す。また、DSCカーブ(第一のDSC測定法)を図4に示す。
前記のプロピレン・エチレン・1-ブテン共重合体(PEBR-2)90wt%、アイソタクティックポリプロピレン(PP)10wt%を、ラボプラストミル(東洋精機製)にて混練(190℃、3min、40rpm)し、軟質ポリプロピレン樹脂組成物(X2)を得た。軟質ポリプロピレン樹脂組成物(X2)の物性を表2に示す。また、DSCカーブ(第一のDSC測定法)を図5に示す。
前記のプロピレン・エチレン共重合体(PER)85wt%、アイソタクティックポリプロピレン(PP)15wt%を、ラボプラストミル(東洋精機製)にて混練(190℃、3min、40rpm)し、軟質ポリプロピレン樹脂組成物(X3)を得た。軟質ポリプロピレン樹脂組成物(X3)の物性を表2に示す。また、DSCカーブ(第一のDSC測定法)を図6に示す。
住友化学製 タフセレン(登録商標)(銘柄名:T-1712)を用い、これを軟質ポリプロピレン樹脂組成物(X4)とした。軟質ポリプロピレン樹脂組成物(X4)の物性を表2に示す。また、DSCカーブ(第一のDSC測定法)を図7に示す。
融点Tm(A-X)およびTm(B-X)および融解エンタルピーΔH(A-X)、ΔH(B-X)は、前記した『本発明に関する第1のDSC測定方法およびDSC曲線作成方法』に基づいて解析した。なおパーキンエルマー社製の測定装置を用い、試験体は、ショアーA硬度測定に用いたものと同一の条件で作成した3mm厚みのプレスシートを試験前に23℃±2℃で2週間の状態調節を行ったものを用いた。
ショアーA硬度測定に用いたものと同一の条件で作成した2mm厚みのプレスシートを、日本電色工業(株)製のデジタル濁度計「NDH-2000」、C光源を用いてシクロヘキサノール溶液中で拡散透過光量および全透過光量を測定し、下式により内部ヘイズ、全光線透過率を計算した。
全光線透過率=100×(全透過光量)/(入射光量)
[ショアーA硬度]
プロピレンコポリマー(A)のショアーA硬度測定法(既述)と同一方法を採用した。
プロピレンコポリマー(A)のMFR測定法(既述)と同一方法を採用した。
実施例または比較例に記載の方法で調製した接着剤組成物を用い、190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して3mm厚みのプレスシートを作成した。
実施例または比較例に記載の方法で調製した接着剤組成物を用い、190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して2mm厚みのプレスシートを作成した。
この残留歪値が低いほどゴム弾性を有することを意味する。
実施例または比較例に記載の方法で調製した接着剤組成物を用い、190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して2mm厚みのプレスシートを作成した。
実施例または比較例に記載の方法で調製した接着剤組成物を用い、190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して2mm厚みのプレスシートを作成した。
実施例または比較例に記載の方法で調製した接着剤組成物を、卓上ハンドプレス(190℃)を用いてこれをステンレス板(SUS304-BA板、50mm×100mm、94g)に張り合わせて接着試験サンプルを作成した(接着剤厚み=400μm、接着幅=10mm、図9参考)。
実施例または比較例に記載の方法で調製した接着剤組成物を用い、190℃に設定した油圧式熱プレス成形機を用いて5分余熱した後2分間加圧、すぐに20℃に設定した冷却槽で4分間冷却して2mm厚みのプレスシートを作成した。
全光線透過率=100×(全透過光量)/(入射光量)
[固化速度(結晶化速度)]
固化速度については、DSC測定において観測される結晶化温度Tcをもって評価した。このときの結晶化温度Tcは以下の『本発明に関する第3のDSC測定方法およびDSC曲線作成方法』に基づいて解析し、降温速度20℃/minで200℃から-20℃まで冷却している間に観測される最大の発熱ピークをTcとした。
DSC測定装置内で10分間200℃保持した後、降温速度20℃/minで-20℃まで冷却し、-20℃で1分間保持した後、再度昇温速度20℃/minで200℃まで加熱することでDSC曲線を作成した。
軟質ポリプロピレン樹脂組成物(X1)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-1を得た。接着剤組成物(Y)-1の評価結果を表3に示す。
軟質ポリプロピレン樹脂組成物(X1)40重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)60重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-2を得た。接着剤組成物(Y)-2の評価結果を表3に示す。
軟質ポリプロピレン樹脂組成物(X2)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-3を得た。接着剤組成物(Y)-3の評価結果を表3に示す。
軟質ポリプロピレン樹脂組成物(X2)40重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)60重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-4を得た。接着剤組成物(Y)-4の評価結果を表3に示す。
実施例1で用いた軟質ポリプロピレン樹脂組成物(X1)の代わりに先のプロピレン・エチレン共重合体(PER)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-5を得た。接着剤組成物(Y)-5の評価結果を表3に示す。
実施例1で用いた軟質ポリプロピレン樹脂組成物(X1)の代わりに先のプロピレン・1-ブテン共重合体(PBR)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-6を得た。接着剤組成物(Y)-6の評価結果を表3に示す。
実施例1で用いた軟質ポリプロピレン樹脂組成物(X1)の代わりに先の軟質ポリプロピレン樹脂組成物(X3)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-7を得た。接着剤組成物(Y)-7の評価結果を表3に示す。
実施例1で用いた軟質ポリプロピレン樹脂組成物(X1)の代わりに先の軟質ポリプロピレン樹脂組成物(X4)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部を、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y)-8を得た。接着剤組成物(Y)-8の評価結果を表3に示す。
軟質ポリプロピレン樹脂組成物(X1)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部と、(X1)および(C)の合計量100重量部に対し、低分子量プロピレン重合体(D1)としてポリプロピレンワックス(三井化学製、銘柄名:NP055、190℃における溶融粘度52mPa・s)30重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y2)-1を得た。接着剤組成物(Y2)-1の評価結果を表4に示す。なお、ポリプロピレンワックスの溶融粘度はブルックフィールド型粘度計により、190℃の値を測定した。
軟質ポリプロピレン樹脂組成物(X1)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部と、(X1)および(C)の合計量100重量部に対し、低分子量プロピレン重合体(D2)としてAPAO(ハンツマン製、銘柄名:RT2180、190℃における溶融粘度8000mPa・s)30重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y2)-2を得た。接着剤組成物(Y2)-1の評価結果を表4に示す。なお、APAOの溶融粘度はブルックフィールド型粘度計により、190℃の値を測定した。
実施例5で用いた軟質ポリプロピレン樹脂組成物(X1)のかわりに軟質ポリプロピレン樹脂組成物(X3)60重量部、さらに粘着付与剤(C)(脂環族飽和炭化水素樹脂、荒川化学製、商標:アルコン P-125)40重量部と、(X1)および(C)の合計量100重量部に対し、低分子量プロピレン重合体(D1)としてポリプロピレンワックス(三井化学製、銘柄名:NP055、190℃における溶融粘度52mPa・s)30重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(190℃、5min、60rpm)して接着剤組成物(Y2)-2を得た。接着剤組成物(Y2)-1の評価結果を表4に示す。なお、ポリプロピレンワックスの溶融粘度はブルックフィールド型粘度計により、190℃の値を測定した。
ASTMD1238に準拠し、230℃、2.16kg荷重下で測定した。
比較参考例または参考例に記載の接着剤組成物を用いて、190℃に設定した油圧式熱プレス成形機を用いて3分余熱した後、3分間加圧、すぐに20℃に設定した冷却槽で3分間冷却して2mm厚みのプレスシートを作製した。これより幅5mm、長さ40mmの試験片を作製し、粘弾性測定装置(ティー・エイ・インスツルメント社製、RSA-III)を用いて測定した。具体的には、室温下で試験片の上下端を20mmとなるようにチャック治具で軽く固定し、-40℃に冷却後しっかりと固定した。100℃まで昇温させ温度が安定した後、0.1MPaの張力を加え、30分後のクリープ量(%)を測定した。
軟質ポリプロピレン樹脂組成物(X1)を用いた。評価結果を表5に示す。
軟質ポリプロピレン樹脂組成物(X1)80重量部、さらに低分子量プロピレン重合体(D2)としてAPAO(ハンツマン製、銘柄名:RT2180、190℃における溶融粘度8000mPa・s、融点Tm152℃、融解エンタルピーΔHm32.5J/g)20重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(200℃、10min、40rpm)して組成物(Z)-1を得た。組成物(Z)-1の評価結果を表5に示す。
軟質ポリプロピレン樹脂組成物(X1)60重量部、さらに低分子量プロピレン重合体(D2)としてAPAO(ハンツマン製、銘柄名:RT2180、190℃における溶融粘度8000mPa・s、融点Tm152℃、融解エンタルピーΔHm32.5J/g)40重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(200℃、10min、40rpm)して組成物(Z)-2を得た。組成物(Z)-2の評価結果を表5に示す。
軟質ポリプロピレン樹脂組成物(X2)を用いた。評価結果を表5に示す。
軟質ポリプロピレン樹脂組成物(X2)80重量部、さらに低分子量プロピレン重合体(D2)としてAPAO(ハンツマン製、銘柄名:RT2180、190℃における溶融粘度8000mPa・s、融点Tm152℃、融解エンタルピーΔHm32.5J/g)20重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(200℃、10min、40rpm)して組成物(Z)-3を得た。組成物(Z)-3の評価結果を表5に示す。
軟質ポリプロピレン樹脂組成物(X2)60重量部、さらに低分子量プロピレン重合体(D2)としてAPAO(ハンツマン製、銘柄名:RT2180、190℃における溶融粘度8000mPa・s、融点Tm152℃、融解エンタルピーΔHm32.5J/g)40重量部を配合したものを、ラボプラストミル(東洋精機製)にて混練(200℃、10min、40rpm)して組成物(Z)-4を得た。組成物(Z)-4の評価結果を表5に示す。
Claims (12)
- 下記要件(A1)~(A8)を満たすプロピレンコポリマー(A)40~98重量%、下記要件(B1)~(B3)を満たす結晶性アイソタクティックポリプロピレン(B)2~60重量%からなる軟質ポリプロピレン樹脂組成物(X)10~70重量部と、
粘着付与剤(C)30~90重量部(ここで成分(X)と成分(C)の合計量を100重量部とする)からなる接着剤組成物(Y)。
(A1)ショアーA硬度が20~90の範囲にある。
(A2)プロピレン由来の構成単位を51~90モル%、エチレン由来の構成単位を7~24モル%、炭素数4~20のα-オレフィン由来の構成単位を3~25モル%含むプロピレンとエチレンと炭素数4~20のα-オレフィンとの共重合体である(ここでプロピレン由来の構成単位とエチレン由来の構成単位と炭素数4~20のαオレフィン由来の構成単位の合計を100モル%とする)。
(A3)ゲルパーミエーションクロマトグラフィー(GPC)により測定した重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.2~3.5である。
(A4)13C-NMRにより算出したアイソタクティックトライアッド分率(mm)が85~99.9%である。
(A5)下記式(1)で定義されるB値が0.8~1.3である。
(式中、MOEは、プロピレンとエチレンの連鎖と炭素数4以上のα-オレフィンとエチレンの連鎖の合計の、全ダイアッドに対するモル分率を表し、MOはプロピレンと炭素数4以上のα-オレフィンのモル分率の合計を表し、MEはエチレンのモル分率を表す。)
(A6)13C-NMR測定において解析される、全プロピレン挿入中のプロピレンモノマーの2,1-結合量が1%未満である。
(A7)ガラス転移温度(Tg)が-10℃~-50℃の範囲に観測される。
(A8)MFR(ASTMD1238、230℃、2.16kg荷重)が0.5~500g/10minである。
(B1)示差走査熱量計(DSC)測定装置内で10分間200℃保持した後、降温速度10℃/minで-20℃まで冷却し、-20℃で1分間保持した後、再度昇温速度10℃/minで測定したときに得られるDSC測定によって観測される融点Tm(B)が100~175℃である。
(B2)アイソタクティックペンタッド分率(mmmm)が90~99.8%である。
(B3)メルトフローレート(MFR)(ASTMD1238、230℃、2.16kg荷重下)が0.1~100g/10minである。 - プロピレンコポリマー(A)がさらに下記(A9)および(A10)から選ばれる一つ以上の要件を満たすことを特徴とする請求項1に記載の接着剤組成物(Y)。
(A9)23℃±2℃で72時間以上の状態調節を実施した後の試験体にて、-40℃以下まで冷却してから昇温速度10℃/minで測定したときに得られる示差走査熱量計(DSC)曲線において、融解ピークTm(A)1が30~80℃に観測される。
(A10)23℃±2℃で72時間以上の状態調節を実施した後の試験体を、-40℃以下まで冷却してから昇温速度3℃/minで測定したときの動的固体粘弾性測定において、23℃~40℃における貯蔵弾性率が1MPa~100MPaの範囲にある。 - 軟質ポリプロピレン樹脂組成物(X)が下記要件(X1)を満たすことを特徴とする請求項1または2に記載の接着剤組成物(Y)。
(X1)23℃±2℃で72時間以上の状態調節を実施した後の試験体にて、-40℃以下まで冷却してから昇温速度10℃/minで測定したときの示差走査熱量計(DSC)曲線において、30~80℃に融解ピークTm(A-X)を有し、さらに100~175℃に融解ピークTm(B-X)を示す。 - 軟質ポリプロピレン樹脂組成物(X)がさらに下記要件(X2)を満たすことを特徴とする請求項1~3のいずれかに記載の接着剤組成物(Y)。
(X2)23℃±2℃で72時間以上の状態調節を実施した後の試験体にて、-40℃以下まで冷却してから昇温速度10℃/minで測定したときの示差走査熱量計(DSC)曲線において、融解ピークTm(A-X)を与える転移熱(融解エンタルピー)ΔH(A-X)が0.5~20J/g、融解ピークTm(B-X)を与える転移熱(融解エンタルピー)ΔH(B-X)が3~80J/gである。 - 軟質ポリプロピレン樹脂組成物(X)がさらに下記要件(X3)を満たすことを特徴とする請求項1~4のいずれかに記載の接着剤組成物(Y)。
(X3)2mmtプレスシートの内部ヘイズが0.1~30%かつ全光線透過率が75~99.9%である。 - 請求項1~5のいずれかに記載の接着剤組成物(Y)100重量部に、190℃での溶融粘度が1~15000mPa・sの低分子量プロピレン重合体(D)を5~1000重量部配合してなる接着剤組成物(Y2)。
- 請求項1~5のいずれかに記載の接着剤組成物(Y)100重量部に、190℃での溶融粘度が1~15000mPa・sの低分子量プロピレン重合体(D)を5~150重量部配合してなる接着剤組成物(Y2)。
- 前記低分子量プロピレン重合体(D)が、アイソタクティックポリプロピレン系重合体もしくはアタクテッィクポリプロピレン系重合体であることを特徴とする請求項6または7に記載の接着剤組成物(Y2)。
- 請求項1~5のいずれかに記載の接着剤組成物(Y)からなるホットメルト型接着剤。
- 請求項6~8のいずれかに記載の接着剤組成物(Y2)からなるホットメルト型接着剤。
- 請求項1~5のいずれかに記載の接着剤組成物(Y)からなる感圧型接着剤。
- 請求項6~8のいずれかに記載の接着剤組成物(Y2)からなる感圧型接着剤。
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JPWO2010032600A1 (ja) | 2012-02-09 |
KR101281896B1 (ko) | 2013-07-03 |
EP2327750A4 (en) | 2011-12-07 |
KR20110048074A (ko) | 2011-05-09 |
CN102159660B (zh) | 2013-10-16 |
EP2327750A1 (en) | 2011-06-01 |
US20110172348A1 (en) | 2011-07-14 |
EP2327750B1 (en) | 2013-03-27 |
CN102159660A (zh) | 2011-08-17 |
JP5438682B2 (ja) | 2014-03-12 |
US9273202B2 (en) | 2016-03-01 |
WO2010032600A8 (ja) | 2010-08-05 |
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