WO2006038540A1

WO2006038540A1 - Coating composition

Info

Publication number: WO2006038540A1
Application number: PCT/JP2005/018078
Authority: WO
Inventors: Masato Akimoto; Chiharu Agawa
Original assignee: Cemedine Co., Ltd.
Priority date: 2004-10-04
Filing date: 2005-09-30
Publication date: 2006-04-13
Also published as: JP2006131865A; JP4855675B2

Abstract

Disclosed is a nonaqueous coating composition which enables to obtain a coating with excellent contamination resistance in outdoor exposure by providing the surface with hydrophilic properties. Specifically disclosed is a nonaqueous coating composition wherein 0.5-30 parts by weight, preferably 1-20 parts by weight of a silicone surfactant (b) is blended per 100 parts by weight of a polymer (a) having a hydrolyzable silicon group. The nonaqueous coating composition may preferably further contain an inorganic filler (c) having a particle size of 0.2-4.0 mm. It is also preferable that 0.5-10 parts by weight of an amino silane (d) is blended per 100 parts by weight of the polymer (a) having a hydrolyzable silicon group.

Description

Specification

Paint composition

Technical field

TECHNICAL FIELD [0001] The present invention relates to a resinous resin composition, and more particularly to a low-contamination non-aqueous coating composition with little contamination after coating.

Background art

[0002] Conventionally, the surface of industrial products such as ceramic materials, steel, construction, and building materials has been coated with a synthetic resin paint to impart a design effect and improve weather resistance and corrosion resistance. However, these paints are exposed to wind, rain, dust, and sunlight as time passes after painting, and the surface of the paint is contaminated. In recent years, dirt in structures has been seen as a problem mainly in urban areas, and there is a demand for improvement in pollution resistance.

Patent Document 1: Japanese Patent Laid-Open No. 2003-238795

Patent Document 2: Japanese Unexamined Patent Publication No. 2000-169544

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-059782

Patent Document 4: Japanese Patent Laid-Open No. 2004-51830

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-138151

Patent Document 6: Japanese Patent Laid-Open No. 2001-40037

Disclosure of the invention

Problems to be solved by the invention

[0003] The present invention solves the above-mentioned problems associated with the prior art, and an object of the present invention is to provide a composition for a non-aqueous paint that is excellent in stain resistance in outdoor exposure by imparting hydrophilicity to the surface. To do.

Means for solving the problem

[0004] The present inventors have added (b) 0.5 to 30 parts by weight of (b) a silicone-based surfactant to 100 parts by weight of a polymer having a hydrolyzable silicon group. Has been found to be hydrophilic and has led to the present invention.

That is, the non-aqueous coating composition of the present invention comprises (a) a polymer having a hydrolyzable silicon group 1 00 parts by weight (b) Silicone surfactant 0.5-30 parts by weight, more preferably 1-2

0 weight part is mix | blended, It is characterized by the above-mentioned.

[0006] The polymer (a) having a hydrolyzable silicon group preferably contains a (meth) acrylic polymer having a hydrolyzable silicon group. In the present invention, acryl and methacryl are collectively referred to as (meth) acryl.

[0007] The non-aqueous coating composition of the present invention preferably comprises (c) an inorganic filler having a particle diameter of 0.2 to 4. Omm.

[0008] In addition, it is preferable that (d) a silane force pulling agent 0.5 to: LO part by weight is further blended with 100 parts by weight of the polymer having (a) a hydrolyzable silicon group. . It is preferred that the silane coupling agent (d) is an aminosilane.

The invention's effect

[0009] According to the composition for a non-aqueous coating material of the present invention, hydrophilicity can be imparted to the surface, so that the effect of excellent stain resistance in outdoor exposure can be achieved. BEST MODE FOR CARRYING OUT THE INVENTION

[0010] Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical spirit of the present invention.

[0011] The coating composition of the present invention is a non-aqueous coating composition comprising (a) a polymer having a hydrolyzable silicon group and (b) a silicone surfactant.

Component of coating composition of the present invention (a) The polymer having a hydrolyzable silicon group has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and forms a siloxane bond. An organic polymer containing a crosslinkable silicon-containing group, that is, a hydrolyzable silicon group is used.

[0013] The hydrolyzable silicon group is not particularly limited, but 1 to 6 hydrolyzable silicon groups are generally contained in the molecule. The position of the crosslinkable silyl group is not particularly limited, and may be at the end of the organic polymer molecular chain or inside or both, but it is preferably at the end of the molecular chain. Furthermore, the hydrolyzable silicon group is preferably one represented by the following general formula (1) which is easy to crosslink and easy to produce.

[0014] [Chemical 1] Si— X _n

[In the formula (1), R is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. Most preferred is a methyl group, preferably an aralkyl group of 7 to 20. When a plurality of R are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group, and a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group are selected. Preferred is a methoxy group, with an alkoxy group being more preferred. When there are multiple Xs, they may be the same or different. n is 1, 2 or 3, with 2 being most preferred. ]

[0016] When there are a plurality of hydrolyzable silicon groups in the polymer (a) having hydrolyzable silicon groups, these may be the same or different, and The number of n in formula (1) may be the same or different. Two or more organic polymers having different hydrolyzable silicon groups may be used.

[0017] The polymer in the polymer (a) having a hydrolyzable silicon group is not particularly limited. For example, as disclosed in Patent Documents 1 to 6 and the like, each main chain contains an organosiloxane. Polyoxyalkylene polymer, vinyl-modified polyoxyalkylene polymer, (meth) acryl-modified polyoxyalkylene polymer, (meth) aryl polymer, bull polymer, polyester polymer , (Meth) acrylic acid ester polymers, polyisobutylene polymers and copolymers thereof can be mentioned as preferred examples, and (meth) acrylic polymers are particularly preferred. These polymers (a) may be used alone or in combination of two or more. Specifically, a polyoxyalkylene polymer having a hydrolyzable silicon group, a (meth) acrylic polymer having a hydrolyzable silicon group, a (meth) acryl-modified polyoxyalkylene system having a hydrolyzable silicon group Preferred examples include polymers and mixtures thereof.

[0018] The polymer (a) having a hydrolyzable silicon group preferably contains a (meth) acrylic polymer having a hydrolyzable silicon group from the viewpoint of weather resistance. The hydrolyzable silicon group From the viewpoint of weather resistance, it is preferable to use a (meth) acrylic polymer having

In order to improve physical properties such as workability and elongation, a mixture of the (meth) acrylic polymer having a hydrolyzable silicon group and an organic polymer having another hydrolyzable silicon group is used. It is preferable. Specifically, from the viewpoint of weather resistance, the polymer (a) having a hydrolyzable silicon group is a (meth) acrylic polymer having a hydrolyzable silicon group, or the hydrolyzable silicon group. A (meth) acrylic polymer having an organic polymer having other hydrolyzable silicon groups, preferably a polyoxyalkylene polymer having hydrolyzable silicon groups, The content of the (meth) acrylic polymer having a hydrolyzable silicon group is preferably 10% to 100% by weight, more preferably 50% to 100% by weight. More preferably, it is from 100% by weight. In addition, the point of physical properties such as elongation and workability is such that the content of the polyoxyalkylene polymer having a hydrolyzable silicon group in the polymer (a) having a hydrolyzable silicon group is 10% by weight to 100%. It is preferably 30% by weight to 100% by weight, more preferably 60% by weight to 100% by weight.

[0019] The (meth) acrylic polymer having a hydrolyzable silicon group is more preferably a (meth) acrylic organic polymer having a hydrolyzable silicon group at the molecular chain end. The production method of the (meth) acrylic polymer having a hydrolyzable silicon group at the end is not particularly limited, but the atom transfer radical which is preferred to the living radical polymerization method is preferred to the controlled radical polymerization method. The polymerization method is more preferred.

[0020] A method for producing the polymer (a) having a hydrolyzable silicon group is not particularly limited, and a known synthesis method can be used. When the hydrolyzable silicon group-containing organic polymer contains a hydrolyzable silicon group and the main chain is a vinyl polymer such as an acrylic polymer, a vinyl synthesized by a radical polymerization method is used. It is preferable to use a polymer

[0021] The radical polymerization method is a general radical in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide, or the like as a polymerization initiator. It can be divided into a polymerization method and a controlled radical polymerization method in which a specific functional group can be introduced at a controlled position such as a terminal. In the present invention, it is synthesized by a controlled radical polymerization method. The vinyl polymer thus obtained is more effective.

[0022] The controlled radical polymerization method further includes a chain transfer agent method in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group; It can be divided into living radical polymerization methods in which the terminal grows without causing a termination reaction.

[0023] The living radical polymerization method can obtain a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity, and a monomer having a specific functional group can be introduced at an arbitrary position. Therefore, it is particularly preferable. In the present invention, in addition to the polymerization in which the terminal always has activity and the molecular chain grows and grows, the terminal deactivated and the activated one grow while being in an equilibrium state. Many pseudo-living polymerizations are also included in living polymerization.

[0024] Living radical polymerization methods include a method using a cobalt porphyrin complex, a method using a radical scavenger such as a nitroxide compound, a transition metal complex using an organic halogen compound or a halogenated sulfonyl compound as an initiator. Atom Transfer Radical Polymerization (ATRP), which polymerizes bulle monomers using the catalyst as a catalyst. The living radical polymerization method is not particularly limited, but the atom transfer radical polymerization method is preferable. In the present invention, a reverse atom transfer radical polymerization method, that is, a high acid state when a normal atom transfer radical polymerization catalyst generates a radical, for example, when Cu (I) is used as a catalyst, is used. Also included in the atom transfer radical polymerization method is a method in which a general radical initiator such as peroxide is allowed to act on Cu (II '), and as a result, an equilibrium similar to that of atom transfer radical polymerization is generated. Is.

[0025] As the chain transfer agent method, a halogen-terminated hydrocarbon is used as a chain transfer agent to obtain a halogen-terminated polymer, or a hydroxyl group-containing mercabtan has a hydroxyl group-containing polysulfide as a chain transfer agent. And a method for obtaining a hydroxyl-terminated polymer.

[0026] For example, radical polymerization of a butyl monomer mainly composed of an acrylic monomer using an organic halide or a halogenated sulfo-ruly compound as an initiator and a transition metal complex as a catalyst. As a result, an acrylic polymer having a halogen at the terminal is produced. The (meth) acrylic polymer having a hydrolyzable silicon group used in the present invention at the molecular chain end is This can be obtained by converting the halogen of the acrylic polymer having a halogen at its terminal into a hydrolyzable silicon group. The conversion method is not particularly limited, and a known method can be used.

[0027] The number average molecular weight of the hydrolyzable silicon group-containing polymer (a) is preferably 3,000 to 30,000, more preferably 5,000 to 20,000, and generally a modified silicone resin. What can be called. Specific examples of these include product name Cyril SAT200 and MS polymer MA903 manufactured by Kanechi Co., Ltd., and product name KUSTER S3630 manufactured by Asahi Glass Co., Ltd. and the like.

[0028] Component (b) silicone surfactant of the coating composition of the present invention includes, for example, dimethylsiloxane and polyalkylene oxide as the main chain, and methylsiloxane is a hydrophobic group and alkylene oxide is a hydrophilic group. Examples of ionic surfactants include side-chain-modified copolymers with Si-C bonds or terminal-modified polymers with Si-O-C bonds with respect to the dimethylsiloxane main chain. These products are produced by adjusting the silicon concentration, the chain length of the dimethylsiloxane portion, the type of alkylene oxide, etc., and are also sold as silicone surfactants, foam stabilizers for urethane foam, antifoaming agents, etc. . Specific examples of these include Silwet L7604, FZ2162, and FZ 2207 from Nippon Car Company.

[0029] The silicone-based surfactant (b) is preferably blended in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the polymer (a) having the hydrolyzable silicon group. If the amount is less than 5 parts by weight, the hydrophilic effect of the paint surface is low. If it exceeds 30 parts by weight, there is a problem in terms of water-resistant adhesion to the substrate. Furthermore, with respect to 100 parts by weight of component (a), 1 to 20 parts by weight of component (b) is excellent in terms of stain resistance after coating and adhesion to a substrate.

[0030] The design of the coating surface can be enhanced by blending the powder with the coating composition of the present invention. As the powder, either inorganic powder or organic powder can be used, and (c) an inorganic filler having a particle size of 0.2 to 4. Omm is particularly preferable. Specific examples of the inorganic filler (c) include calcium carbonate, silica sand, and glass beads. These may be used alone or in combination of two or more. The blending ratio of the inorganic filler (c) is not particularly limited and may be appropriately selected as necessary. However, 10 to 500 parts by weight of 100 parts by weight of the component (a) is blended. It is preferable that 50 to 400 parts by weight is more preferable.

[0031] Adhesion can be further improved by blending the silane coupling agent (d) with the coating composition of the present invention. Examples of the silane coupling agent (d) include aminosilanes represented by the following formula (2), γ-glycidoxypropyltrimethoxysilane and the like.

Examples include isocyanate silanes such as topropyltrimethoxysilane, and aminosilanes are particularly preferable. These silane coupling agents may be used alone or in combination of two or more.

[0032] Y- Si- (OZ) · · · (2)

Three

[Wherein Y is an NH group and an alkyl group that may contain a Z or NH bond,

2

An aryl group, an alkoxyalkyl group, and a cycloalkyl group, and Z represents an alkyl group having 1 to 6 carbon atoms. The three Zs may be the same or different. ]

[0033] Specific examples of the aminosilanes include N-β- (aminoethyl) aminopropyltrimethoxysilane, Ν-β- (aminoethyl) aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminoethyla. And minopropylmethyldimethoxysilane. Examples of commercially available products include “ΚΒΜ603” and ΓΚΒΜ903] (manufactured by Shin-Etsu Chemical Co., Ltd.). These aminosilanes may be used alone or in combination of two or more. Aminosilanes and other silane coupling agents may be used in combination.

[0034] When the aminosilanes are ketiminized, it is preferable to block all primary amines among them with a carboxylic compound. Examples of the carboxylic compound include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0035] The mixing ratio of the silane coupling agent (d) is not particularly limited, but it is preferable to add 0.5 to L0 parts by weight with respect to 100 parts by weight of the component (a). It is more preferable to mix the ingredients.

[0036] An epoxy resin can be further added to the coating composition of the present invention for the purpose of improving water-resistant adhesion. Polymers having hydrolyzable silicon groups as other compounding agents (a) Curing catalysts, curing accelerators, curing retarders, plasticizers, fillers, adhesion-imparting agents, diluents, pigments, dehydrants, UV absorbers, light stabilizers, antioxidants, etc. Possible Example

Hereinafter, the power to specifically explain the present invention by way of examples. These examples are shown by way of example, and should not be construed in a limited manner.

(Examples 1 to 4 and Comparative Examples 1 to 3)

According to the composition shown in Table 1, each component was mixed at room temperature and reduced pressure using a high viscosity mixing stirrer to obtain a coating composition.

[0039] [Table 1]

[0040] The compounding amounts of the compounding substances in Table 1 are expressed in parts by weight, and * 1 to * 13 are as follows.

* 1: SAT200 (manufactured by Kanechi Co., Ltd.)

* 2: MA903 (manufactured by Kanechi Co., Ltd.)

* 3: Silwet L 7604 (Nippon Tunica)

* 4: Chamui stone 3mm (particle size 1. Omm) * 5: Silica sand No. 5 (particle size 2.4 mm)

* 6: KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.)

* 7: Whiten SB (Shiraishi Kogyo Co., Ltd., particle size 0.002mm)

* 8: Exester 3020 (Asahi Glass Co., Ltd., molecular weight 3,000)

* 9: ADK STAB LA36 (Asahi Denka Co., Ltd.)

* 10: ADK STAB LA62 (Asahi Denka Co., Ltd.)

* 11: KBM1003 (Shin-Etsu Chemical Co., Ltd.)

* 12: Neostan U—100 (Nitto Kosei Co., Ltd.)

* 13: R820 (Ishihara Sangyo Co., Ltd.)

The obtained coating composition was evaluated as follows, and the results are shown in Table 2.

1. Adhesion

In accordance with JIS K 5600 paint general test method adhesion (cross-cut method), measured under the following conditions: substrate; mortar plate, coating thickness: lmm, curing; 23 ° C 50% RH X 7 days, cut interval: 2mm . The state of the surface of the coating film was observed, and the number of lattice meshes without peeling was shown in Table 2.

[0042] 2. Contact angle

A specimen was obtained by the same method as in the adhesion test. A 0.2 cc water droplet was dropped on the coating film of the test specimen obtained at room temperature, and the contact angle at which the water droplet contacted the coating film was measured 1 minute later.

[0043] 3. Pollution resistance

A specimen was obtained by the same method as in the adhesion test. After the exposed specimen was exposed on the roof for 3 months, its raindrop contamination was observed and judged visually according to the following criteria:

◎: The rain streak is not good! /, ○: The rain streak is slightly closed Δ: The rain streak is considerably closed X: The rain streak is noticeably attached.

[0044] 4. Designability

A specimen was obtained by the same method as in the adhesion test. The roughness of the coating film of the obtained specimen was visually observed. The evaluation criteria are as follows.

A: The degree of roughness is large, ◯: There is a feeling of roughness, and △: A smooth surface without the feeling of roughness. [0045] [Table 2]

[0046] The coating compositions of Examples 1 to 4 as shown in Table 2 are excellent in stain resistance in outdoor exposure, and were formulated with an inorganic filler having a particle size of 0.2 to 4. Omm. Examples 1 and 2 also had good design properties.

Industrial applicability

[0047] The coating composition of the present invention is excellent in stain resistance, design and adhesion, and can be suitably used as a coating for industrial products such as ceramic materials, steel, construction and building materials.

Claims

The scope of the claims

[1] A composition for a non-aqueous coating comprising (a) 100 parts by weight of a polymer having a hydrolyzable silicon group and (b) 0.5 to 30 parts by weight of a silicone surfactant.

[2] The composition for non-aqueous paint according to claim 1, wherein 1 to 20 parts by weight of (b) silicone surfactant is blended with 100 parts by weight of the polymer having (a) hydrolyzable silicon group. object.

[3] The non-aqueous coating composition according to claim 1 or 2, further comprising (c) an inorganic filler having a particle size of 0.2 to 4. Omm.

[4] The force according to any one of claims 1 to 3, wherein (d) 0.5 to 10 parts by weight of a silane coupling agent is further blended with 100 parts by weight of the polymer having (a) a hydrolyzable silicon group. The composition for non-aqueous paints described in the item.