WO2013151006A1 - Resin composition, paint using same, and article painted with paint - Google Patents
Resin composition, paint using same, and article painted with paint Download PDFInfo
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- WO2013151006A1 WO2013151006A1 PCT/JP2013/059913 JP2013059913W WO2013151006A1 WO 2013151006 A1 WO2013151006 A1 WO 2013151006A1 JP 2013059913 W JP2013059913 W JP 2013059913W WO 2013151006 A1 WO2013151006 A1 WO 2013151006A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Definitions
- the present invention relates to a resin composition having excellent storage stability.
- the present invention also relates to a paint using the resin composition and an article coated with the paint.
- the problem to be solved by the present invention is to provide a resin composition having excellent storage stability that hardly changes in viscosity even when stored for a long period of time and does not easily cause gelation.
- Another object of the present invention is to provide a paint that is excellent in initial curability using the resin composition and from which a coating film having high surface hardness can be obtained, and further provides an article coated with the paint.
- the present inventors have polymerized a monomer having a specific hydrolyzable silyl group and a monomer having an amino group as essential monomer components. And the alcohol-containing resin composition has excellent storage stability, and the paint using the composition is found to have excellent initial curability at room temperature, thus completing the invention. .
- the present invention comprises a polymer (A) obtained by polymerizing a monomer (a1) represented by the following general formula (I) and a monomer (a2) having an amino group as essential monomer components;
- the present invention relates to a resin composition containing alcohol (B).
- the present invention also relates to a paint using the composition and an article coated with the paint.
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alkyl group
- R 3 is a hydrogen atom or an alkyl group
- n is an integer of 1 to 6
- the resin composition of the present invention has very excellent storage stability, it can be used for paints even after long-term storage. Further, when used in a paint, a paint having excellent initial curability at room temperature can be obtained. Therefore, it is very useful as a paint for coating various articles.
- the resin composition of the present invention comprises a polymer (A) obtained by polymerizing the monomer (a1) represented by the following general formula (I) and the monomer (a2) having an amino group as essential monomer components. And alcohol (B).
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alkyl group
- R 3 is a hydrogen atom or an alkyl group
- n is an integer of 1 to 6
- the monomer (a1) is represented by the general formula (I).
- R 2 in the general formula (I) is an alkyl group, and specific examples thereof include an alkyl group having 1 to 6 carbon atoms. In view of the availability of raw materials, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is particularly preferred.
- R 3 in the general formula (I) is a hydrogen atom or an alkyl group. Among them, examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms. Among these alkyl groups, an alkyl group having 1 to 4 carbon atoms is preferable because initial curability is further improved, and a methyl group or an ethyl group is particularly preferable.
- n is an integer of 1 to 6, but n is preferably an integer of 2 to 4, particularly preferably n is 3 (propylene group) in view of availability of raw materials. .
- the monomer (a2) is a monomer having an amino group.
- the amino group may be any of a primary amino group (—NH 2 ), a secondary amino group (—NHR), and a tertiary amino group (—NR′R ′′). Tertiary amino groups are preferred because they can further improve storage stability
- Specific examples of the monomer (a2) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth).
- N, N-dialkylaminoalkyl (meth) acrylates such as acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N- (N, N-dimethylaminoethyl) ( (Meth) acrylamide, N- (N, N-diethylaminoethyl) (meth) acrylamide, N- (N, N-dimethylaminopropyl) ( T) acrylamide, N- (N, N-dialkylaminoalkyl) (meth) acrylamide such as N- (N, N-diethylaminopropyl) (meth) acrylamide; tert-butylaminoethyl (meth) acrylate, tert-butylamino Tert-butylaminoalkyl (meth) acrylates such as propyl (meth) acrylate
- Alkyl (meth) acrylate etc.
- N, N-dialkylaminoalkyl (meth) acrylate, N- (N, N-dialkylaminoalkyl) (meth) acrylamide is preferred because of improved curability.
- these monomers (a2) may also be used in combination of two or more be used alone.
- (meth) acrylate refers to one or both of methacrylate and acrylate
- (meth) acrylamide refers to one or both of methacrylamide and acrylamide
- (meth) acryloyl “Means one or both of methacryloyl and acryloyl,” (meth) acrylonitrile "means one or both of methacrylonitrile and acrylonitrile,” (meth) acrylic acid "means methacrylic acid and acrylic acid Or one of both.
- the polymer (A) is obtained by polymerizing the monomer (a1) and the monomer (a2) as essential monomer components, but other monomers other than these monomers ( a3) may be used.
- examples of such other monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, and n-butyl (meth).
- the polymer (A) can be produced by a known polymerization method using the monomer (a1) and the monomer (a2), and, if necessary, other monomers (a3) as raw materials. Although it can be performed, the solution radical polymerization method is preferred because it is the simplest.
- the solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is performed in the presence of a polymerization initiator.
- the solvent that can be used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, iso-propanol, n-butanol, iso-butanol, sec-butanol.
- Alcohol solvents such as ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-butyl, acetic acid-isobutyl, and amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Is mentioned. These solvents can be used alone or in combination of two or more.
- Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-Bis (4,4-ditert-octyl Peroxyketal compounds such as -oxycyclohexyl) propane and 2,2-bis (4,
- a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, ⁇ -methylstyrene dimer or the like as a molecular weight regulator.
- a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, ⁇ -methylstyrene dimer or the like as a molecular weight regulator.
- the component ratio derived from the monomer (a1) in the polymer (A) is preferably in the range of 0.1 to 50% by mass, 0
- the range of 0.5 to 30% by mass is more preferable, the range of 1 to 10% by mass is more preferable, and the range of 2 to 5% by mass is particularly preferable.
- the component ratio derived from the monomer (a2) in the polymer (A) is preferably in the range of 0.1 to 60% by mass, more preferably in the range of 0.5 to 30% by mass.
- the range of 20% by mass is more preferable, and the range of 5 to 15% by mass is particularly preferable.
- the remainder of the component ratio derived from the said monomer (a1) in the said polymer (A) and the component ratio derived from the said monomer (a2) is The component ratio is derived from the monomer (a3).
- the alcohol (B) used in the resin composition of the present invention is a hydrocarbon compound having a hydroxyl group, for example, a straight chain such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like.
- Alcohol; cycloaliphatic alcohols such as cyclohexanol, cyclooctanol, cyclododecanol and the like can be mentioned.
- alcohols having 1 to 10 carbon atoms are preferable, alcohols having 1 to 6 carbon atoms are more preferable, and carbon atoms Alcohols having a number in the range of 1 to 4 are more preferred, and methanol and n-butanol are particularly preferred. These alcohols (B) can be used alone or in combination of two or more. These alcohols (B) may be used as the alcohol (B) leaving the solvent used in the production of the polymer (A) as it is.
- the paint of the present invention contains the above-described resin composition of the present invention and a curing agent (C).
- the curing agent (C) is preferably a compound having at least one functional group selected from the group consisting of an epoxy group, a silanol group and a hydrolyzable silyl group.
- a compound (C1) having an epoxy group and a hydrolyzable silyl group in one molecule a polyepoxy compound, since it has excellent curability and a strong coating film can be obtained.
- the compounds (C3) having a hydrolyzable silyl group and / or silanol group other than (C2) and the compound (C1) those which are at least one compound or a mixture thereof are preferred.
- Examples of the compound (C1) include silane compounds having an epoxy group. Moreover, as a hydrolysable silyl group which the said compound (C1) has, the functional group represented by the following general formula (II) is mentioned, for example.
- R 1 is a hydrogen atom, an alkyl group, an aralkyl group, an alkoxyl group, a phenoxy group, an iminooxy group or an alkenyloxy group
- R 2 is a halogen atom, an alkoxyl group, a phenoxy group, an iminooxy group or an alkenyloxy group.
- A is an integer of 0 to 2.
- Specific examples of the compound (C1) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltriisosilane.
- Silane compounds such as propenyloxysilane and ⁇ -glycidoxypropyltriiminooxysilane; adducts of the above silane compounds and glycidol; addition of silane compounds having amino groups such as ⁇ -aminopropyltrimethoxysilane and diepoxy compounds Such as things.
- ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriisopropenyloxysilane are preferable because of excellent curability.
- the compound (C2) is a compound having two or more epoxy groups in one molecule.
- a compound (C2) is preferably a glycidyl ether of a polyhydric alcohol, specifically, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether. , Pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and the like.
- a resin having two or more epoxy groups in one molecule can also be used as the compound (C2).
- Examples of such a resin include glycidyl (meth) acrylate, (meth) acrylic acid ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate), styrene, vinyl acetate, vinyl chloride, and the like.
- examples thereof include acrylic resins obtained by copolymerization with monomers.
- the compound (C3) include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraoctoxysilane, tetrakis (2-methoxyethoxy) silane, tetra Benzyloxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, vinyltrimethoxysilane Alkoxysilane compounds such as vinyltriethoxysilane and ⁇ -chloropropyltrimethoxysilane; ⁇ -mercaptopropyltri
- the compound (C3) a partial hydrolysis condensate of the above silane compound; the above-mentioned ⁇ -methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ⁇ -methacryloxypropyltriacetoxysilane, etc.
- a homopolymer of the monomer having a hydrolyzable silyl group that can be used as the compound (C3) or a copolymer with a monomer copolymerizable with the monomer will be further described.
- the monomer having a hydrolyzable silyl group include ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropylmethyldimethoxysilane, and ⁇ - (meth) acryloyloxypropyltriisosilane.
- the body is mentioned.
- the thing equivalent to the said monomer (a3) can be used.
- the same method as the method for producing the polymer (A) can be used.
- a curing catalyst (D) may be added as necessary for the purpose of improving curability.
- the curing catalyst (D) include basic compounds such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methylate; tetraisopropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, octylic acid.
- Metal-containing compounds such as cobalt, zinc octylate, calcium octylate, lead cabtenate, cobalt naphthenate, diptyltin diacetate, dibutyltin dioctoate, diptyltin dilaurate, diptyltin simarate: p-toluenesulfonic acid, tricumylacetic acid, phosphoric acid And acidic compounds such as monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid and dialkyl phosphorous acid.
- the paints of the present invention include organic pigments, inorganic pigments, anti-splitting agents (pigment dispersants), antistatic agents, antifoaming agents, viscosity modifiers (flow modifiers), light-resistant stabilizers, and weather-resistant stabilizers.
- Various additives such as heat stabilizers, UV absorbers, antioxidants, leveling agents; fiber derivatives such as nitrocellulose and cellulose acetate butyrate; chlorinated polyethylene, chlorinated polypropylene, petroleum resins, chlorinated rubber, etc. Resin can be added.
- the coating material of the present invention is excellent in initial curability and has a high surface hardness, it is possible to prevent damage to the surface of the article by coating the coating material on the surface of various articles.
- articles that can be coated with the paint of the present invention include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines.
- Body Housing for OA equipment such as printers, facsimiles, etc .;
- Various plastic parts such as various parts used for interior materials of various vehicles such as automobiles and railway vehicles; Woodwork materials such as furniture, artificial and synthetic leather; FRP bathtubs It is done.
- Interior and exterior materials for buildings such as exterior walls, roofs, glass, and decorative panels; civil engineering members such as soundproof walls and drainage grooves; galvanized steel sheets used for household appliances, industrial machinery, automotive parts, and aluminum-zinc Metal members such as plated steel plates such as alloy steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates are also included.
- the coating method of the paint of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, screen printing , Spray, applicator, bar coater and the like.
- examples of a method for forming a cured coating film after applying the paint of the present invention include a method of heating and drying in the range of room temperature to about 80 ° C.
- Example 1 A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 55 parts by mass of xylene and 15 parts by mass of n-butanol, heated to 80 ° C. in a nitrogen atmosphere, and then 40 parts by mass of methyl methacrylate.
- ABS-E 2,2′-azobis (2-methylbutyronitrile)
- the polymer (A-1) solution is referred to as a resin composition (1).
- Examples 2 to 4 and Comparative Examples 1 to 3 Polymers (A-2) to (A-4) and (R-1) to (R) were used in the same manner as in Example 1 except that the amount of each monomer used was changed to the amount shown in Table 1. A 50% by weight solution of R-3) was obtained.
- the solutions of the polymers (A-2) to (A-4) and (R-1) to (R-3) are referred to as resin compositions (2) to (7), respectively. Further, in the same manner as in Example 1, the storage stability of the resin compositions (2) to (7) was evaluated.
- Table 1 shows the monomer composition of each polymer, the solvent composition in each resin composition, and the evaluation results of the storage stability of each resin composition.
- Comparative Example 1 is an example in which the monomer (a1) represented by the general formula (I) was not used, but had storage stability that was not substantially different from the resin composition of the present invention. I understood.
- Comparative Examples 2 and 3 are examples using a monomer in which R 2 is an alkoxyl group in the general formula (I), but there was no problem in storage stability at 20 ° C. for 1 month. It was found that thickening and gelation occurred during storage at 20 ° C. for 3 months and at 40 ° C., resulting in poor storage stability. In Comparative Examples 2 and 3, which were inferior in storage stability, the preparation of the paint and the evaluation of the paint described later were not performed.
- Example 5 100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)), 7 parts by mass of ⁇ -glycidoxypropyltrimethoxysilane and tetraethoxysilane (hereinafter referred to as “the polymer (A-1)”) 6 parts by mass of a partially hydrolyzed condensate (abbreviated as “TEOS”) (“ethyl silicate 40” manufactured by Colcoat Co., Ltd.) was uniformly mixed to obtain a paint (1).
- TEOS partially hydrolyzed condensate
- Example 6 to 8 Instead of the resin composition (1) used in Example 1, the resin compositions (2) to (4) obtained in Examples 2 to 4 (polymers (A-2) to (A-4)) A paint (2) to (4) was obtained in the same manner as in Example 1 except that a 50% by mass solution) was used. Using the obtained coating material, production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
- Example 9 To the coating material (1) obtained in Example 1, 0.5 part by weight of dibutyltin dioctate was added as a curing catalyst to obtain a coating material (5). Using this paint (5), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
- Example 10 100 parts by mass of resin composition (1) obtained in Example 1 (50% by mass solution of polymer (A-1)), polyepoxy compound (“Deconal EX-411” manufactured by Nagase ChemteX Corporation) 9 parts by mass and 6 parts by mass of TEOS partially hydrolyzed condensate (“Ecosilicate 40” manufactured by Colcoat Co., Ltd.) were uniformly mixed to obtain paint (6). Using this paint (6), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
- Polyepoxy compound (“Deconal EX-411” manufactured by Nagase ChemteX Corporation) 9 parts by mass and 6 parts by mass of TEOS partially hydrolyzed condensate (“Ecosilicate 40” manufactured by Colcoat Co., Ltd.) were uniformly mixed to obtain paint (6).
- this paint (6) production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of
- Example 11 100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)) and 100 parts by mass of the compound (C4-1) obtained in Synthesis Example 1 were uniformly added. By mixing, paint (7) was obtained. Using this paint (7), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
- Table 2 shows the compositions and evaluation results of the paints (1) to (8) obtained in Examples 5 to 11 and Comparative Example 4 above.
- Comparative Example 4 is an example of a paint using a resin composition containing a polymer not using the monomer (a1) represented by the general formula (I).
- the pencil hardness is H, which has a surface hardness that is not substantially different from that of the paint of the present invention, but the gel fraction at 3 hours after the formation of the cured coating film was as low as 47%, indicating that the initial curability was inferior.
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Abstract
Provided is a resin composition characterized by containing a polymer (A) and an alcohol (B), the polymer (A) being obtained by polymerizing a monomer (a1) represented by general formula (I) and a monomer (a2) having an amino group as essential monomer components. This resin composition exhibits little change in viscosity even when stored for prolonged periods of time, has highly exceptional storage stability with minimal incidence of gelling, and excellent initial curability when used at room temperature, and can accordingly be suitably used as a paint. A variety of articles can be painted with the paint to obtain an article having a cured coating of high surface hardness (R1 is a hydrogen atom or methyl group, R2 is an alkyl group, R3 is a hydrogen atom or alkyl group, and n is an integer of 1 to 6).
Description
本発明は、保存安定性に優れた樹脂組成物に関するものである。また、該樹脂組成物を用いた塗料及び該塗料で塗装された物品に関するものである。
The present invention relates to a resin composition having excellent storage stability. The present invention also relates to a paint using the resin composition and an article coated with the paint.
従来において、塩基性窒素原子を有するビニル系単量体を必須の単量体成分とするビニル系重合体と、硬化剤として１分子中にエポキシ基及び加水分解性シリル基を有する化合物と含有する塗料用樹脂組成物が提案されており、常温で容易に硬化し、その硬化塗膜は耐候性、付着性に優れることが知られている（例えば、特許文献１、２参照。）。しかし、この塗料用樹脂組成物は、初期硬化性が劣り、硬度、耐溶剤性が一定レベルに達するのに時間がかかるという欠点があった。
Conventionally, it contains a vinyl polymer having a vinyl monomer having a basic nitrogen atom as an essential monomer component, and a compound having an epoxy group and a hydrolyzable silyl group in one molecule as a curing agent. A resin composition for paints has been proposed, and is easily cured at room temperature, and the cured coating film is known to have excellent weather resistance and adhesion (see, for example, Patent Documents 1 and 2). However, this coating resin composition has the disadvantages that initial curability is poor and it takes time to reach a certain level of hardness and solvent resistance.
しかし、これら公報に記載の組成物を使用して塗膜を形成させた場合、前記の問題点を解決するため、ビニル系重合体に加水分解性シリル基を有するビニル系単量体を用いる手法が提案されている（例えば、特許文献３、４参照。）。しかしながら、前記技術を我々が検証したところ、確かに初期の硬化性は向上するものの、塗膜の構成成分であるビニル系重合体自体の保存安定性が非常に悪く、実用に耐えうるものではなかった。
However, when a coating film is formed using the composition described in these publications, a method using a vinyl monomer having a hydrolyzable silyl group in a vinyl polymer in order to solve the above-mentioned problems Has been proposed (see, for example, Patent Documents 3 and 4). However, as a result of our verification of the above technology, the initial curability is certainly improved, but the storage stability of the vinyl polymer itself, which is a component of the coating film, is very poor and cannot be practically used. It was.
本発明が解決しようとする課題は、長期保存しても粘度変化が少なく、ゲル化も生じにくい保存安定性に優れた樹脂組成物を提供することである。また、該樹脂組成物を用いた初期硬化性に優れ、高い表面硬度を有する塗膜が得られる塗料を提供し、さらには、該塗料を塗装した物品を提供することである。
The problem to be solved by the present invention is to provide a resin composition having excellent storage stability that hardly changes in viscosity even when stored for a long period of time and does not easily cause gelation. Another object of the present invention is to provide a paint that is excellent in initial curability using the resin composition and from which a coating film having high surface hardness can be obtained, and further provides an article coated with the paint.
本発明者等は、上記の課題を解決するため鋭意研究した結果、特定の加水分解性シリル基を有する単量体及びアミノ基を有する単量体を必須の単量体成分として重合した重合体と、アルコールとを含有する樹脂組成物は、優れた保存安定性を有し、さらに、該組成物を用いた塗料は、常温での初期の硬化性に優れることを見出し、発明を完成させた。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have polymerized a monomer having a specific hydrolyzable silyl group and a monomer having an amino group as essential monomer components. And the alcohol-containing resin composition has excellent storage stability, and the paint using the composition is found to have excellent initial curability at room temperature, thus completing the invention. .
すなわち、本発明は、下記一般式（Ｉ）で表される単量体（ａ１）及びアミノ基を有する単量体（ａ２）を必須の単量体成分として重合した重合体（Ａ）と、アルコール（Ｂ）とを含有することを特徴とする樹脂組成物に関する。また、該組成物を用いた塗料及び該塗料で塗装された物品に関する。
That is, the present invention comprises a polymer (A) obtained by polymerizing a monomer (a1) represented by the following general formula (I) and a monomer (a2) having an amino group as essential monomer components; The present invention relates to a resin composition containing alcohol (B). The present invention also relates to a paint using the composition and an article coated with the paint.
本発明の樹脂組成物は、非常に優れた保存安定性を有するため、長期保存しても塗料等に使用可能である。また、塗料に用いた際には、常温での初期の硬化性が優れた塗料が得られる。したがって、各種物品を塗装する塗料として非常に有用である。
Since the resin composition of the present invention has very excellent storage stability, it can be used for paints even after long-term storage. Further, when used in a paint, a paint having excellent initial curability at room temperature can be obtained. Therefore, it is very useful as a paint for coating various articles.
本発明の樹脂組成物は、下記一般式（Ｉ）で表される単量体（ａ１）及びアミノ基を有する単量体（ａ２）を必須の単量体成分として重合した重合体（Ａ）と、アルコール（Ｂ）とを含有するものである。
The resin composition of the present invention comprises a polymer (A) obtained by polymerizing the monomer (a1) represented by the following general formula (I) and the monomer (a2) having an amino group as essential monomer components. And alcohol (B).
前記単量体（ａ１）は、前記一般式（Ｉ）で表されるものである。前記一般式（Ｉ）中のＲ２は、アルキル基であるが、具体的には、炭素原子数１～６のアルキル基が挙げられる。また、原料入手の容易性から、炭素原子数１～３のアルキル基が好ましく、特にメチル基が好ましい。前記一般式（Ｉ）中のＲ３は水素原子又はアルキル基であるが、このうちアルキル基としては、炭素原子数１～６のアルキル基が挙げられる。このアルキル基の中でも、初期硬化性がより向上することから、炭素原子数１～４のアルキル基が好ましく、特にメチル基又はエチル基が好ましい。前記一般式（Ｉ）中のｎは１～６の整数であるが、原料入手の容易性から、ｎが２～４の整数のものが好ましく、特にｎが３（プロピレン基）のものが好ましい。
The monomer (a1) is represented by the general formula (I). R 2 in the general formula (I) is an alkyl group, and specific examples thereof include an alkyl group having 1 to 6 carbon atoms. In view of the availability of raw materials, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is particularly preferred. R 3 in the general formula (I) is a hydrogen atom or an alkyl group. Among them, examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms. Among these alkyl groups, an alkyl group having 1 to 4 carbon atoms is preferable because initial curability is further improved, and a methyl group or an ethyl group is particularly preferable. In the general formula (I), n is an integer of 1 to 6, but n is preferably an integer of 2 to 4, particularly preferably n is 3 (propylene group) in view of availability of raw materials. .
前記単量体（ａ２）は、アミノ基を有する単量体である。このアミノ基は、１級アミノ基（－ＮＨ２）、２級アミノ基（－ＮＨＲ）及び３級アミノ基（－ＮＲ’Ｒ”）のいずれでも構わないが、これらの中でも、樹脂組成物の保存安定性をより向上できることから、３級アミノ基が好ましい。前記単量体（ａ２）の具体例としては、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート等のＮ，Ｎ－ジアルキルアミノアルキル（メタ）アクリレート；Ｎ－（Ｎ，Ｎ－ジメチルアミノエチル）（メタ）アクリルアミド、Ｎ－（Ｎ，Ｎ－ジエチルアミノエチル）（メタ）アクリルアミド、Ｎ－（Ｎ，Ｎ－ジメチルアミノプロピル）（メタ）アクリルアミド、Ｎ－（Ｎ，Ｎ－ジエチルアミノプロピル）（メタ）アクリルアミド等のＮ－（Ｎ，Ｎ－ジアルキルアミノアルキル）（メタ）アクリルアミド；ｔｅｒｔ－ブチルアミノエチル（メタ）アクリレート、ｔｅｒｔ－ブチルアミノプロピル（メタ）アクリレート等のｔｅｒｔ－ブチルアミノアルキル（メタ）アクリレート；アジリジニルエチル（メタ）アクリレート、ピロリジニルエチル（メタ）アクリレート、ピペリジニルエチル（メタ）アクリレート等の環状アミノ基を有するアルキル（メタ）アクリレートなどが挙げられる。これらの中でも、硬化性がより向上することから、Ｎ，Ｎ－ジアルキルアミノアルキル（メタ）アクリレート、Ｎ－（Ｎ，Ｎ－ジアルキルアミノアルキル）（メタ）アクリルアミドが好ましい。また、これらの単量体（ａ２）は、単独で用いることも２種以上併用することもできる。
The monomer (a2) is a monomer having an amino group. The amino group may be any of a primary amino group (—NH 2 ), a secondary amino group (—NHR), and a tertiary amino group (—NR′R ″). Tertiary amino groups are preferred because they can further improve storage stability Specific examples of the monomer (a2) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth). N, N-dialkylaminoalkyl (meth) acrylates such as acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N- (N, N-dimethylaminoethyl) ( (Meth) acrylamide, N- (N, N-diethylaminoethyl) (meth) acrylamide, N- (N, N-dimethylaminopropyl) ( T) acrylamide, N- (N, N-dialkylaminoalkyl) (meth) acrylamide such as N- (N, N-diethylaminopropyl) (meth) acrylamide; tert-butylaminoethyl (meth) acrylate, tert-butylamino Tert-butylaminoalkyl (meth) acrylates such as propyl (meth) acrylate; cyclic amino groups such as aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, etc. Alkyl (meth) acrylate, etc. Among these, N, N-dialkylaminoalkyl (meth) acrylate, N- (N, N-dialkylaminoalkyl) (meth) acrylamide is preferred because of improved curability. Is preferred Further, these monomers (a2) may also be used in combination of two or more be used alone.
なお、本発明において、「（メタ）アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「（メタ）アクリルアミド」とは、メタクリルアミドとアクリルアミドの一方又は両方をいい、「（メタ）アクリロイル」とは、メタクリロイルとアクリロイルの一方又は両方をいい、「（メタ）アクリロニトリル」とは、メタクリロニトリルとアクリロニトリルの一方又は両方をいい、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいう。
In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, “(meth) acrylamide” refers to one or both of methacrylamide and acrylamide, and “(meth) acryloyl”. "Means one or both of methacryloyl and acryloyl," (meth) acrylonitrile "means one or both of methacrylonitrile and acrylonitrile," (meth) acrylic acid "means methacrylic acid and acrylic acid Or one of both.
前記重合体（Ａ）は、前記単量体（ａ１）及び単量体（ａ２）を必須の単量体成分として重合したものであるが、これらの単量体以外のその他の単量体（ａ３）を用いても構わない。このようなその他の単量体（ａ３）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉｓｏ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸エステル化合物；ジメチルマレート、ジメチルフマレート、ジブチルフマレート、ジメチルイタコネート等の不飽和二塩基酸のジアルキルエステル化合物；（メタ）アクリル酸、モノブチルマレート、モノブチルフマレート、クロトン酸、マレイン酸、フマル酸、イタコン酸等のカルボキシル基を有するビニル単量体；無水マレイン酸、無水イタコン酸等の酸無水基を有するビニル単量体；（メタ）アクリロニトリル等のシアノ基を有するビニル単量体；（メタ）アクリル酸のヒドロキシアルキルエステルと燐酸又は燐酸エステルとの縮合生成物；ｐ－スチレンスルホン酸、２－アクリルアミド－２－メチル－プロパンスルホン酸等のスルホン酸基を有するビニル単量体；酢酸ビニル、安息香酸ビニル、「ベオバ」（オランダ国シエル社製のビニルエステル）等のビニルエステル化合物；「ビスコート８Ｆ、８ＦＭ、３Ｆ又は３ＦＭ」（大阪有機化学株式会社製の含フッ素（メタ）アクリルモノマー）、パーフルオロシクロヘキシル（メタ）アクリレート、ジ－パーフルオロシクロヘキシルフマレート、Ｎ－ｉｓｏ－プロピルパーフルオロオクタンスルホンアミドエチル（メタ）アクリレート等のフッ素化アルキル基を有するビニル単量体；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、クロロトリフルオロエチレン等のハロゲン化オレフィン；スチレン、α－メチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、ビニルトルエン等の芳香族ビニル単量体などが挙げられる。これらは、単独で用いることも２種以上併用することもできる。
The polymer (A) is obtained by polymerizing the monomer (a1) and the monomer (a2) as essential monomer components, but other monomers other than these monomers ( a3) may be used. Examples of such other monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, and n-butyl (meth). Acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) ) (Meth) acrylate compounds such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; dimethyl malate, dimethyl fumarate, di Dialkyl ester compounds of unsaturated dibasic acids such as tilfumarate and dimethyl itaconate; having a carboxyl group such as (meth) acrylic acid, monobutyl malate, monobutyl fumarate, crotonic acid, maleic acid, fumaric acid, itaconic acid Vinyl monomers; vinyl monomers having acid anhydride groups such as maleic anhydride and itaconic anhydride; vinyl monomers having cyano groups such as (meth) acrylonitrile; hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid Or a condensation product with a phosphate ester; a vinyl monomer having a sulfonic acid group such as p-styrenesulfonic acid or 2-acrylamido-2-methyl-propanesulfonic acid; vinyl acetate, vinyl benzoate, “Veoba” (Netherlands) Vinyl ester compounds such as “vinyl ester manufactured by Kiel Ciel Co., Ltd.”; , 8FM, 3F or 3FM "(fluorine-containing (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate, N-iso-propyl perfluorooctanesulfonamide Vinyl monomers having a fluorinated alkyl group such as ethyl (meth) acrylate; Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene; styrene, α-methylstyrene, p -Aromatic vinyl monomers such as tert-butylstyrene and vinyltoluene. These can be used alone or in combination of two or more.
前記重合体（Ａ）の製造方法としては、前記単量体（ａ１）及び単量体（ａ２）、さらには必要に応じてその他の単量体（ａ３）を原料として、公知の重合方法で行うことができるが、溶液ラジカル重合法が最も簡便であることから好ましい。
The polymer (A) can be produced by a known polymerization method using the monomer (a1) and the monomer (a2), and, if necessary, other monomers (a3) as raw materials. Although it can be performed, the solution radical polymerization method is preferred because it is the simplest.
上記の溶液ラジカル重合法は、原料である各単量体を溶剤に溶解し、重合開始剤存在下で重合反応を行う方法である。この際に用いることができる溶剤としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ－ヘキサン、オクタン等の炭化水素系溶剤；メタノール、エタノール、ｉｓｏ－プロパノール、ｎ－ブタノール、ｉｓｏ－ブタノール、ｓｅｃ－ブタノール、エチレングリコールモノメチルエーテル等のアルコール系溶剤；酢酸メチル、酢酸エチル、酢酸－ｎ－ブチル、酢酸－イソブチル、酢酸アミル等のエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤などが挙げられる。これらの溶剤は、単独で用いることも２種以上併用することもできる。
The solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is performed in the presence of a polymerization initiator. Examples of the solvent that can be used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, iso-propanol, n-butanol, iso-butanol, sec-butanol. Alcohol solvents such as ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-butyl, acetic acid-isobutyl, and amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Is mentioned. These solvents can be used alone or in combination of two or more.
前記重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド等のケトンパーオキサイド化合物；１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔｅｒｔ－ブチルパーオキシ）バレレート、２，２－ビス（４，４－ジｔｅｒｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－ヘキシルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジクミルパーオキシシクロヘキシル）プロパン等のパーオキシケタール化合物；クメンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド等のハイドロパーオキサイド化合物；１，３－ビス（ｔｅｒｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、ジイソプロピルベンゼンパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド等のジアルキルパーオキサイド化合物；デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド化合物；ビス（ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ－ブチルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン等のパーオキシエステル化合物などの有機過酸化物と、２，２’－アゾビスイソブチロニトリル、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）等のアゾ化合物などが挙げられる。
Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-Bis (4,4-ditert-octyl Peroxyketal compounds such as -oxycyclohexyl) propane and 2,2-bis (4,4-dicumylperoxycyclohexyl) propane; cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide Hydroperoxide compounds such as 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, dialkyl peroxide compounds such as tert-butyl cumyl peroxide; diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; bis (tert Peroxycarbonate compounds such as butylcyclohexyl) peroxydicarbonate; organic peroxides such as peroxyester compounds such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane And azo compounds such as 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), etc. It is done.
また、前記重合開始剤とともに、必要に応じて、分子量調節剤としてラウリルメルカプタン、オクチルメルカプタン、２－メルカプトエタノール、チオグリコール酸オクチル、３－メルカプトプロピオン酸、α－メチルスチレン・ダイマー等の連鎖移動剤も用いることができる。
In addition to the polymerization initiator, if necessary, a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, α-methylstyrene dimer or the like as a molecular weight regulator. Can also be used.
本発明の樹脂組成物の保存安定性をより向上できることから、前記重合体（Ａ）中の前記単量体（ａ１）由来の成分比率は、０．１～５０質量％の範囲が好ましく、０．５～３０質量％の範囲がより好ましく、１～１０質量％の範囲がさらに好ましく、２～５質量％の範囲が特に好ましい。
Since the storage stability of the resin composition of the present invention can be further improved, the component ratio derived from the monomer (a1) in the polymer (A) is preferably in the range of 0.1 to 50% by mass, 0 The range of 0.5 to 30% by mass is more preferable, the range of 1 to 10% by mass is more preferable, and the range of 2 to 5% by mass is particularly preferable.
また、前記重合体（Ａ）中の前記単量体（ａ２）由来の成分比率は、０．１～６０質量％の範囲が好ましく、０．５～３０質量％の範囲がより好ましく、１～２０質量％の範囲がさらに好ましく、５～１５質量％の範囲が特に好ましい。本発明の樹脂組成物をより無色にしたい場合は、前記重合体（Ａ）中の前記単量体（ａ２）由来の成分比率をなるべく少なくすることが好ましい。
The component ratio derived from the monomer (a2) in the polymer (A) is preferably in the range of 0.1 to 60% by mass, more preferably in the range of 0.5 to 30% by mass. The range of 20% by mass is more preferable, and the range of 5 to 15% by mass is particularly preferable. In order to make the resin composition of the present invention more colorless, it is preferable to reduce the component ratio derived from the monomer (a2) in the polymer (A) as much as possible.
また、前記単量体（ａ３）を用いる場合は、上記の前記重合体（Ａ）中の前記単量体（ａ１）由来の成分比率及び前記単量体（ａ２）由来の成分比率の残部が前記単量体（ａ３）由来の成分比率となる。
Moreover, when using the said monomer (a3), the remainder of the component ratio derived from the said monomer (a1) in the said polymer (A) and the component ratio derived from the said monomer (a2) is The component ratio is derived from the monomer (a3).
本発明の樹脂組成物に用いるアルコール（Ｂ）は、水酸基を有する炭化水素化合物であり、例えば、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール等の直鎖状アルコール；シクロヘキサノール、シクロオクタノール、シクロドデカノール等の脂環式アルコールなどが挙げられる。これらのアルコール（Ｂ）の中でも、保存安定性がより向上することから、炭素原子数が１～１０の範囲のアルコールが好ましく、炭素原子数が１～６の範囲のアルコールがより好ましく、炭素原子数が１～４の範囲のアルコールがさらに好ましく、メタノール、ｎ－ブタノールが特に好ましい。また、これらのアルコール（Ｂ）は、単独で用いることも２種以上併用することもできる。なお、これらのアルコール（Ｂ）は、前記重合体（Ａ）の製造時に用いる溶剤をそのまま残して、アルコール（Ｂ）として用いても構わない。
The alcohol (B) used in the resin composition of the present invention is a hydrocarbon compound having a hydroxyl group, for example, a straight chain such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like. Alcohol; cycloaliphatic alcohols such as cyclohexanol, cyclooctanol, cyclododecanol and the like can be mentioned. Among these alcohols (B), since the storage stability is further improved, alcohols having 1 to 10 carbon atoms are preferable, alcohols having 1 to 6 carbon atoms are more preferable, and carbon atoms Alcohols having a number in the range of 1 to 4 are more preferred, and methanol and n-butanol are particularly preferred. These alcohols (B) can be used alone or in combination of two or more. These alcohols (B) may be used as the alcohol (B) leaving the solvent used in the production of the polymer (A) as it is.
本発明の塗料は、上記の本発明の樹脂組成物と、硬化剤（Ｃ）を含有するものである。前記硬化剤（Ｃ）は、エポキシ基、シラノール基及び加水分解性シリル基からなる群から選ばれる少なくとも１種の官能基を有する化合物が好ましい。また、このような硬化剤（Ｃ）の中でも、硬化性に優れ、強固な塗膜が得られることから、１分子中にエポキシ基及び加水分解性シリル基を有する化合物（Ｃ１）、ポリエポキシ化合物（Ｃ２）、及び前記化合物（Ｃ１）以外の加水分解性シリル基及び／又はシラノール基を有する化合物（Ｃ３）のうち、少なくとも１種の化合物、又はこれらの混合物であるものが好ましい。
The paint of the present invention contains the above-described resin composition of the present invention and a curing agent (C). The curing agent (C) is preferably a compound having at least one functional group selected from the group consisting of an epoxy group, a silanol group and a hydrolyzable silyl group. Further, among such curing agents (C), a compound (C1) having an epoxy group and a hydrolyzable silyl group in one molecule, a polyepoxy compound, since it has excellent curability and a strong coating film can be obtained. Of the compounds (C3) having a hydrolyzable silyl group and / or silanol group other than (C2) and the compound (C1), those which are at least one compound or a mixture thereof are preferred.
前記化合物（Ｃ１）としては、エポキシ基を有するシラン化合物等が挙げられる。また、前記化合物（Ｃ１）が有する加水分解性シリル基としては、例えば、下記一般式（ＩＩ）で表される官能基が挙げられる。
Examples of the compound (C1) include silane compounds having an epoxy group. Moreover, as a hydrolysable silyl group which the said compound (C1) has, the functional group represented by the following general formula (II) is mentioned, for example.
、
前記化合物（Ｃ１）の具体例としては、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリイソプロペニルオキシシラン、γ－グリシドキシプロピルトリイミノオキシシラン等のシラン化合物；前記シラン化合物とグリシドールとの付加物；γ－アミノプロピルトリメトキシシラン等のアミノ基を有するシラン化合物とジエポキシ化合物との付加物などが挙げられる。これらの中でも、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリイソプロペニルオキシシランは、硬化性に優れることから好ましい。 ,
Specific examples of the compound (C1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriisosilane. Silane compounds such as propenyloxysilane and γ-glycidoxypropyltriiminooxysilane; adducts of the above silane compounds and glycidol; addition of silane compounds having amino groups such as γ-aminopropyltrimethoxysilane and diepoxy compounds Such as things. Among these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriisopropenyloxysilane are preferable because of excellent curability.
前記化合物（Ｃ１）の具体例としては、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリイソプロペニルオキシシラン、γ－グリシドキシプロピルトリイミノオキシシラン等のシラン化合物；前記シラン化合物とグリシドールとの付加物；γ－アミノプロピルトリメトキシシラン等のアミノ基を有するシラン化合物とジエポキシ化合物との付加物などが挙げられる。これらの中でも、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリイソプロペニルオキシシランは、硬化性に優れることから好ましい。 ,
Specific examples of the compound (C1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriisosilane. Silane compounds such as propenyloxysilane and γ-glycidoxypropyltriiminooxysilane; adducts of the above silane compounds and glycidol; addition of silane compounds having amino groups such as γ-aminopropyltrimethoxysilane and diepoxy compounds Such as things. Among these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriisopropenyloxysilane are preferable because of excellent curability.
前記化合物（Ｃ２）は、１分子中に２つ以上のエポキシ基を有している化合物である。このような化合物（Ｃ２）としては、多価アルコールのグリシジルエーテルが好ましく、具体的にはエチレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセリンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。また、１分子中に２つ以上のエポキシ基を有している樹脂も前記化合物（Ｃ２）として用いることができる。このような樹脂としては、例えば、グリシジル（メタ）アクリレートを、（メタ）アクリル酸エステル（例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等）、スチレン、酢酸ビニル、塩化ビニル等の単量体と共重合させて得られるアクリル樹脂などが挙げられる。
The compound (C2) is a compound having two or more epoxy groups in one molecule. Such a compound (C2) is preferably a glycidyl ether of a polyhydric alcohol, specifically, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether. , Pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and the like. A resin having two or more epoxy groups in one molecule can also be used as the compound (C2). Examples of such a resin include glycidyl (meth) acrylate, (meth) acrylic acid ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate), styrene, vinyl acetate, vinyl chloride, and the like. Examples thereof include acrylic resins obtained by copolymerization with monomers.
前記化合物（Ｃ３）の具体例としては、テトラメトキシシラン、トリメトキシシラン、テトラエトキシシラン、トリエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、テトラオクトキシシラン、テトラキス（２－メトキシエトキシ）シラン、テトラベンジルオキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジエトキシシラン、γ－イソシアネートプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－クロロプロピルトリメトキシシラン等のアルコキシシラン化合物；γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリイソプロペニルオキシシラン、γ－メルカプトプロピルトリアセトキシシラン等のメルカプトシラン化合物；γ－アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン等のアミノアルコキシシラン化合物；テトライソプロペニルオキシシラン、フェニルトリイソプロペニルオキシシラン、γ－イソシアネートプロピルトリイソプロペニルオキシシラン、γ－メタクリロキシプロピルトリイソプロペニルオキシシラン、γ－メルカプトプロピルトリイソプロペニルオキシシラン、テトラブテニルオキシシラン等のアルケニルオキシシラン化合物；テトラアセトキシシラン、メチルトリアセトキシシラン、γ－メルカプトプロピルトリアセトキシシラン、テトラプロピオニルオキシシラン、フェニルトリプロピオニルオキシシラン、ビニルトリアセトキシシラン等のアシロキシシラン化合物；テトラクロロシラン、テトラブロモシラン、メチルトリクロロシラン、エチルトリクロロシラン、フェニルトリクロロシラン、ベンジルトリブロモシラン、ジメチルジクロロシラン、ジフェニルジクロロシラン等のハロシラン化合物；テトラキス（ジメチルイミノオキシ）シラン、メチルトリス（ジメチルイミノオキシ）シラン、テトラキス（メチル－エチルイミノオキシ）シラン、γ－メタクリロキシプロピルトリス（ジメチルイミノオキシ）シラン、γ－メルカプトプロピルトリス（ジメチルイミノオキシ）シラン等のイミノオキシシラン化合物などのシラン化合物が挙げられる。
Specific examples of the compound (C3) include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraoctoxysilane, tetrakis (2-methoxyethoxy) silane, tetra Benzyloxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, γ-isocyanatopropyltrimethoxysilane, vinyltrimethoxysilane Alkoxysilane compounds such as vinyltriethoxysilane and γ-chloropropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptotop Mercaptosilane compounds such as pyrtriisopropenyloxysilane and γ-mercaptopropyltriacetoxysilane; aminoalkoxysilane compounds such as γ-aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane; tetraiso Alkenyl such as propenyloxysilane, phenyltriisopropenyloxysilane, γ-isocyanatopropyltriisopropenyloxysilane, γ-methacryloxypropyltriisopropenyloxysilane, γ-mercaptopropyltriisopropenyloxysilane, tetrabutenyloxysilane Oxysilane compounds; tetraacetoxysilane, methyltriacetoxysilane, γ-mercaptopropyltriacetoxysilane, tetrapropionyloxysilane, phenoxy Acyloxysilane compounds such as rutripropionyloxysilane and vinyltriacetoxysilane; halosilanes such as tetrachlorosilane, tetrabromosilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, benzyltribromosilane, dimethyldichlorosilane and diphenyldichlorosilane Compound: Tetrakis (dimethyliminooxy) silane, Methyltris (dimethyliminooxy) silane, Tetrakis (methyl-ethyliminooxy) silane, γ-methacryloxypropyltris (dimethyliminooxy) silane, γ-mercaptopropyltris (dimethyliminooxy) ) Silane compounds such as iminooxysilane compounds such as silane.
また、前記化合物（Ｃ３）として、上記のシラン化合物を部分加水分解縮合物；上記のγ－メタクリロキシプロピルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、γ－メタクリロキシプロピルトリアセトキシシラン等の加水分解性シリル基を有する単量体の単独重合体又は該単量体と共重合可能な単量体との共重合体；多価アルコール、水酸基を有するアクリル樹脂、水酸基を有するアルキド樹脂、水酸基を有するポリエステル樹脂、ポリエーテルポリオール等のポリヒドロキシ化合物と上記のシラン化合物とを、特開昭５８－１６８６２５号公報に開示されている方法に従って反応させて得られる樹脂；不飽和基を有する化合物又は樹脂（ジアリルサクシネート、トリアリルトリメリテート、ジアリルフタレート等のポリアリル化合物、不飽和基を有するビニル系重合体、不飽和基を有するポリエステル樹脂、不飽和基を有するアルキド樹脂等）と、加水分解性シリル基を有するヒドロシラン化合物（トリメトキシシラン、トリエトキシラン等）との付加物；グリシジル（メタ）アクリレート等のエポキシ基を有する単量体を重合した重合体、エポキシ樹脂等のエポキシ基を有する樹脂と上記のメルカプトシラン化合物との付加物；γ－イソシアネートプロピルトリメトキシシラン、γ－イソシアネートプロピルトリイソプロペニルオキシシラン等のイソシアネート基を有するシラン化合物と前記ポリヒドロキシ化合物とを反応させて得られるウレタン樹脂；末端にシラノール基を有するシリコーン樹脂；環状シロキサン構造を有するシラノール化合物（例えば、東レ・ダウコーニング株式会社製「トーレシリコーンＳＨ－６０１８」等）などが挙げられる。
Further, as the compound (C3), a partial hydrolysis condensate of the above silane compound; the above-mentioned γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltriacetoxysilane, etc. A homopolymer of a monomer having a hydrolyzable silyl group or a copolymer of a monomer copolymerizable with the monomer; a polyhydric alcohol, an acrylic resin having a hydroxyl group, an alkyd resin having a hydroxyl group, Resin obtained by reacting a polyhydroxy compound such as a polyester resin having a hydroxyl group and a polyether polyol with the above silane compound according to the method disclosed in JP-A-58-168625; a compound having an unsaturated group Or resin (diallyl succinate, triallyl trimellitate, diallyl Polyallyl compounds such as tarates, vinyl polymers having unsaturated groups, polyester resins having unsaturated groups, alkyd resins having unsaturated groups, etc., and hydrosilane compounds having hydrolyzable silyl groups (trimethoxysilane, Adducts with ethoxylane, etc .; polymers obtained by polymerizing monomers having an epoxy group such as glycidyl (meth) acrylate; adducts with resins having an epoxy group such as epoxy resins and the above mercaptosilane compounds; γ -Urethane resins obtained by reacting silane compounds having an isocyanate group such as isocyanate propyltrimethoxysilane and γ-isocyanatopropyltriisopropenyloxysilane with the polyhydroxy compound; silicone resins having a silanol group at the end; cyclic siloxanes Silanol with structure And compounds (for example, “Toray Silicone SH-6018” manufactured by Toray Dow Corning Co., Ltd.) and the like.
前記化合物（Ｃ３）として用いることのできる前記加水分解性シリル基を有する単量体の単独重合体又は該単量体と共重合可能な単量体との共重合体について、さらに説明する。前記加水分解性シリル基を有する単量体としては、例えば、γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリイソプロペニルオキシシラン、γ－（メタ）アクリロイルオキシプロピルトリイミノオキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニル（トリス－β－メトキシエトキシ）シラン、ビニルトリアセトキシシラン、ビニルトリクロロシラン等の単量体が挙げられる。また、前記加水分解性シリル基を有する単量体単量体と共重合可能な単量体としては、前記単量体（ａ３）と同等のものを用いることができる。
A homopolymer of the monomer having a hydrolyzable silyl group that can be used as the compound (C3) or a copolymer with a monomer copolymerizable with the monomer will be further described. Examples of the monomer having a hydrolyzable silyl group include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, and γ- (meth) acryloyloxypropyltriisosilane. Propenyloxysilane, γ- (meth) acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, etc. The body is mentioned. Moreover, as a monomer copolymerizable with the monomer monomer which has the said hydrolysable silyl group, the thing equivalent to the said monomer (a3) can be used.
また、前記加水分解性シリル基を有する単量体単量体と共重合可能な単量体との共重合は、上記の重合体（Ａ）の製造方法と同様の方法を用いることができる。
Further, for the copolymerization of the monomer having a hydrolyzable silyl group and a copolymerizable monomer, the same method as the method for producing the polymer (A) can be used.
本発明の塗料には、必要に応じて、硬化性を向上する目的で、硬化触媒（Ｄ）を加えても構わない。この硬化触媒（Ｄ）としては、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、ナトリウムメチラート等の塩基性化合物；テトライソプロピルチタネート、テトラブチルチタネート、オクチル酸錫、オクチル酸鉛、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸カルシウム、カブテン酸鉛、ナフテン酸コバルト、ジプチル錫ジアセテート、ジブチル錫ジオクトエート、ジプチル錫ジラウレート、ジプチル錫シマレート等の含金属化合物：ｐ－トルエンスルホン酸、トリクミル酢酸、燐酸、モノアルキル燐酸、ジアルキル燐酸、モノアルキル亜燐酸、ジアルキル亜燐酸等の酸性化合物などが挙げられる。
In the paint of the present invention, a curing catalyst (D) may be added as necessary for the purpose of improving curability. Examples of the curing catalyst (D) include basic compounds such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methylate; tetraisopropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, octylic acid. Metal-containing compounds such as cobalt, zinc octylate, calcium octylate, lead cabtenate, cobalt naphthenate, diptyltin diacetate, dibutyltin dioctoate, diptyltin dilaurate, diptyltin simarate: p-toluenesulfonic acid, tricumylacetic acid, phosphoric acid And acidic compounds such as monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid and dialkyl phosphorous acid.
さらに、本発明の塗料には、有機顔料、無機顔料、色分れ防止剤（顔料分散剤）、帯電防止剤、消泡剤、粘度調整剤（流動調整剤）、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤等の各種の添加剤；ニトロセルロース、セルロースアセテートブチレート等の繊維素誘導体；塩素化ポリエチレン、塩素化ポリプロピレン、石油樹脂、塩化ゴム等の樹脂を添加することができる。
Furthermore, the paints of the present invention include organic pigments, inorganic pigments, anti-splitting agents (pigment dispersants), antistatic agents, antifoaming agents, viscosity modifiers (flow modifiers), light-resistant stabilizers, and weather-resistant stabilizers. , Various additives such as heat stabilizers, UV absorbers, antioxidants, leveling agents; fiber derivatives such as nitrocellulose and cellulose acetate butyrate; chlorinated polyethylene, chlorinated polypropylene, petroleum resins, chlorinated rubber, etc. Resin can be added.
本発明の塗料は、初期硬化性に優れ、表面硬度の高い塗膜が得られることから、該塗料を各種物品の表面に塗装することで、物品表面の傷つきを防止することができる。本発明の塗料を塗装することのできる物品としては、例えば、テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；パソコン、スマートフォン、携帯電話、デジタルカメラ、ゲーム機等の電子機器の筐体；プリンター、ファクシミリ等のＯＡ機器の筐体；自動車、鉄道車輌等の各種車輌の内装材に用いられる各種部品などの各種プラスチック部材；家具等の木工材料、人工・合成皮革；ＦＲＰ浴槽が挙げられる。また、外壁、屋根、ガラス、化粧板等の建築物の内外装材；防音壁、排水溝等の土木部材；家電製品、産業機械、自動車の部品等に使用される亜鉛めっき鋼板、アルミニウム－亜鉛合金鋼板等のめっき鋼板、アルミ板、アルミ合金板、電磁鋼板、銅板、ステンレス鋼板等の金属部材も挙げられる。
Since the coating material of the present invention is excellent in initial curability and has a high surface hardness, it is possible to prevent damage to the surface of the article by coating the coating material on the surface of various articles. Examples of articles that can be coated with the paint of the present invention include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Body: Housing for OA equipment such as printers, facsimiles, etc .; Various plastic parts such as various parts used for interior materials of various vehicles such as automobiles and railway vehicles; Woodwork materials such as furniture, artificial and synthetic leather; FRP bathtubs It is done. Interior and exterior materials for buildings such as exterior walls, roofs, glass, and decorative panels; civil engineering members such as soundproof walls and drainage grooves; galvanized steel sheets used for household appliances, industrial machinery, automotive parts, and aluminum-zinc Metal members such as plated steel plates such as alloy steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates are also included.
本発明の塗料の塗装方法としては、用途により異なるが、例えば、グラビアコーター、ロールコーター、コンマコーター、ナイフコーター、エアナイフコーター、カーテンコーター、キスコーター、シャワーコーター、ホイーラーコーター、スピンコーター、ディッピング、スクリーン印刷、スプレー、アプリケーター、バーコーター等の方法が挙げられる。また、本発明の塗料を塗装後、硬化塗膜とする方法としては、常温～約８０℃の範囲で加熱乾燥させる方法が挙げられる。
The coating method of the paint of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, screen printing , Spray, applicator, bar coater and the like. In addition, examples of a method for forming a cured coating film after applying the paint of the present invention include a method of heating and drying in the range of room temperature to about 80 ° C.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。
Hereinafter, the present invention will be described in more detail with reference to specific examples.
（実施例１）
攪拌装置、温度計、還流冷却管及び窒素導入管を備えた反応器に、キシレン５５質量部、ｎ－ブタノール１５質量部を仕込み、窒素雰囲気中で８０℃に昇温した後、メチルメタクリレート４０質量部、ノルマルブチルアクリレート２０質量部、ｎ－ブチルメタクリレート１８質量部、ジメチルアミノエチルメタクリレート１０質量部、γ－メタクリロキシプロピルメチルジメトキシシラン２質量部、２，２’－アゾビス（２－メチルブチロニトリル）（以下、「ＡＢＮ－Ｅ」と略記する。）０．６質量部及びキシレン５質量部からなる混合物を３時間かけて滴下した。滴下終了後、８０℃に２時間保持した後、さらに、ＡＢＮ－Ｅ ０．２質量部、トルエン１５質量部からなる混合物を１時間で滴下した。次いで、８０℃に１２時間保持したのち、５０℃以下に冷却し、メタノール１５部を添加することで、重合体（Ａ－１）の５０質量％溶液を得た。なお、この重合体（Ａ－１）の溶液を樹脂組成物（１）とする。 Example 1
A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 55 parts by mass of xylene and 15 parts by mass of n-butanol, heated to 80 ° C. in a nitrogen atmosphere, and then 40 parts by mass of methyl methacrylate. Parts, normal butyl acrylate 20 parts by mass, n-butyl methacrylate 18 parts by mass, dimethylaminoethyl methacrylate 10 parts by mass, γ-methacryloxypropylmethyldimethoxysilane 2 parts by mass, 2,2′-azobis (2-methylbutyronitrile) ) (Hereinafter abbreviated as “ABN-E”) A mixture of 0.6 parts by mass and 5 parts by mass of xylene was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 2 hours, and then a mixture composed of 0.2 parts by mass of ABN-E and 15 parts by mass of toluene was added dropwise over 1 hour. Next, after maintaining at 80 ° C. for 12 hours, the mixture was cooled to 50 ° C. or less, and 15 parts of methanol was added to obtain a 50 mass% solution of the polymer (A-1). The polymer (A-1) solution is referred to as a resin composition (1).
攪拌装置、温度計、還流冷却管及び窒素導入管を備えた反応器に、キシレン５５質量部、ｎ－ブタノール１５質量部を仕込み、窒素雰囲気中で８０℃に昇温した後、メチルメタクリレート４０質量部、ノルマルブチルアクリレート２０質量部、ｎ－ブチルメタクリレート１８質量部、ジメチルアミノエチルメタクリレート１０質量部、γ－メタクリロキシプロピルメチルジメトキシシラン２質量部、２，２’－アゾビス（２－メチルブチロニトリル）（以下、「ＡＢＮ－Ｅ」と略記する。）０．６質量部及びキシレン５質量部からなる混合物を３時間かけて滴下した。滴下終了後、８０℃に２時間保持した後、さらに、ＡＢＮ－Ｅ ０．２質量部、トルエン１５質量部からなる混合物を１時間で滴下した。次いで、８０℃に１２時間保持したのち、５０℃以下に冷却し、メタノール１５部を添加することで、重合体（Ａ－１）の５０質量％溶液を得た。なお、この重合体（Ａ－１）の溶液を樹脂組成物（１）とする。 Example 1
A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 55 parts by mass of xylene and 15 parts by mass of n-butanol, heated to 80 ° C. in a nitrogen atmosphere, and then 40 parts by mass of methyl methacrylate. Parts, normal butyl acrylate 20 parts by mass, n-butyl methacrylate 18 parts by mass, dimethylaminoethyl methacrylate 10 parts by mass, γ-methacryloxypropylmethyldimethoxysilane 2 parts by mass, 2,2′-azobis (2-methylbutyronitrile) ) (Hereinafter abbreviated as “ABN-E”) A mixture of 0.6 parts by mass and 5 parts by mass of xylene was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 2 hours, and then a mixture composed of 0.2 parts by mass of ABN-E and 15 parts by mass of toluene was added dropwise over 1 hour. Next, after maintaining at 80 ° C. for 12 hours, the mixture was cooled to 50 ° C. or less, and 15 parts of methanol was added to obtain a 50 mass% solution of the polymer (A-1). The polymer (A-1) solution is referred to as a resin composition (1).
［保存安定性の評価］
上記の実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の溶液）を密閉されたガラス容器に移し、２０℃及び４０℃の雰囲気下で保存した。それぞれの温度で保存したものについて、１か月後及び３か月後の重合体の状態を目視で観察し、以下の基準に従って保存安定性を評価した。
○：粘度変化がなし。
△：やや増粘がみられる。
×：顕著な増粘もしくはゲル化がみられる。 [Evaluation of storage stability]
The resin composition (1) obtained in Example 1 (polymer (A-1) solution) was transferred to a sealed glass container and stored in an atmosphere of 20 ° C. and 40 ° C. About what was preserve | saved at each temperature, the state of the polymer after 1 month and 3 months was observed visually, and the storage stability was evaluated according to the following references | standards.
○: No change in viscosity.
Δ: Slightly thickened.
X: Significant thickening or gelation is observed.
上記の実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の溶液）を密閉されたガラス容器に移し、２０℃及び４０℃の雰囲気下で保存した。それぞれの温度で保存したものについて、１か月後及び３か月後の重合体の状態を目視で観察し、以下の基準に従って保存安定性を評価した。
○：粘度変化がなし。
△：やや増粘がみられる。
×：顕著な増粘もしくはゲル化がみられる。 [Evaluation of storage stability]
The resin composition (1) obtained in Example 1 (polymer (A-1) solution) was transferred to a sealed glass container and stored in an atmosphere of 20 ° C. and 40 ° C. About what was preserve | saved at each temperature, the state of the polymer after 1 month and 3 months was observed visually, and the storage stability was evaluated according to the following references | standards.
○: No change in viscosity.
Δ: Slightly thickened.
X: Significant thickening or gelation is observed.
（実施例２～４及び比較例１～３）
各単量体の使用量を表１に示した量に変更した以外は実施例１と同様に操作して、重合体（Ａ－２）～（Ａ－４）及び（Ｒ－１）～（Ｒ－３）の５０質量％溶液を得た。なお、この重合体（Ａ－２）～（Ａ－４）及び（Ｒ－１）～（Ｒ－３）の溶液をそれぞれ樹脂組成物（２）～（７）とする。また、実施例１と同様に、樹脂組成物（２）～（７）の保存安定性を評価した。 (Examples 2 to 4 and Comparative Examples 1 to 3)
Polymers (A-2) to (A-4) and (R-1) to (R) were used in the same manner as in Example 1 except that the amount of each monomer used was changed to the amount shown in Table 1. A 50% by weight solution of R-3) was obtained. The solutions of the polymers (A-2) to (A-4) and (R-1) to (R-3) are referred to as resin compositions (2) to (7), respectively. Further, in the same manner as in Example 1, the storage stability of the resin compositions (2) to (7) was evaluated.
各単量体の使用量を表１に示した量に変更した以外は実施例１と同様に操作して、重合体（Ａ－２）～（Ａ－４）及び（Ｒ－１）～（Ｒ－３）の５０質量％溶液を得た。なお、この重合体（Ａ－２）～（Ａ－４）及び（Ｒ－１）～（Ｒ－３）の溶液をそれぞれ樹脂組成物（２）～（７）とする。また、実施例１と同様に、樹脂組成物（２）～（７）の保存安定性を評価した。 (Examples 2 to 4 and Comparative Examples 1 to 3)
Polymers (A-2) to (A-4) and (R-1) to (R) were used in the same manner as in Example 1 except that the amount of each monomer used was changed to the amount shown in Table 1. A 50% by weight solution of R-3) was obtained. The solutions of the polymers (A-2) to (A-4) and (R-1) to (R-3) are referred to as resin compositions (2) to (7), respectively. Further, in the same manner as in Example 1, the storage stability of the resin compositions (2) to (7) was evaluated.
各重合体の単量体組成、各樹脂組成物中の溶剤組成、及び各樹脂組成物の保存安定性の評価結果を表１に示す。
Table 1 shows the monomer composition of each polymer, the solvent composition in each resin composition, and the evaluation results of the storage stability of each resin composition.
表１に示した結果から、本発明の樹脂組成物（１）～（４）は、優れた保存安定性を有することが分かった。一方、比較例１は、前記一般式（Ｉ）で表される単量体（ａ１）を用いなかった例であるが、本発明の樹脂組成物とほぼ差がない保存安定性を有することが分かった。比較例２及び３は、前記一般式（Ｉ）において、Ｒ２がアルコキシル基である単量体を用いた例であるが、２０℃で１か月は保存安定性に問題はなかったが、２０℃で３か月及び４０℃での保存において増粘やゲル化を生じ、保存安定性に劣ることが分かった。なお、保存安定性に劣った比較例２及び３のものは、後述する塗料の調製及び塗料の評価を行わなかった。
From the results shown in Table 1, it was found that the resin compositions (1) to (4) of the present invention have excellent storage stability. On the other hand, Comparative Example 1 is an example in which the monomer (a1) represented by the general formula (I) was not used, but had storage stability that was not substantially different from the resin composition of the present invention. I understood. Comparative Examples 2 and 3 are examples using a monomer in which R 2 is an alkoxyl group in the general formula (I), but there was no problem in storage stability at 20 ° C. for 1 month. It was found that thickening and gelation occurred during storage at 20 ° C. for 3 months and at 40 ° C., resulting in poor storage stability. In Comparative Examples 2 and 3, which were inferior in storage stability, the preparation of the paint and the evaluation of the paint described later were not performed.
（合成例１）
攪拌装置、温度計、還流冷却管及び窒素導入管を備えた反応器に、トルエン８００質量部及びｎ－ブタノール５００質量部を仕込み、窒素雰囲気下で１１０℃に昇温した後、スチレン２００質量部、ｎ－ブチルメタクリレート３００質量部、γ－メタクリロキシプロピルトリメトキシシラン５００質量部、トリブチルホスフィンオキサイド（ＴＢＰＯ）４０質量部及びトルエン２００質量部からなる混合物を８時間かけて滴下した。滴下終了後、さらに、１１０℃に１５時間保持することで、不揮発分の化合物（Ｃ４－１）の４０質量％溶液を得た。 (Synthesis Example 1)
A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 800 parts by mass of toluene and 500 parts by mass of n-butanol, heated to 110 ° C. in a nitrogen atmosphere, and then 200 parts by mass of styrene. A mixture of 300 parts by mass of n-butyl methacrylate, 500 parts by mass of γ-methacryloxypropyltrimethoxysilane, 40 parts by mass of tributylphosphine oxide (TBPO) and 200 parts by mass of toluene was added dropwise over 8 hours. After completion of the dropping, the solution was further maintained at 110 ° C. for 15 hours to obtain a 40% by mass solution of the non-volatile compound (C4-1).
攪拌装置、温度計、還流冷却管及び窒素導入管を備えた反応器に、トルエン８００質量部及びｎ－ブタノール５００質量部を仕込み、窒素雰囲気下で１１０℃に昇温した後、スチレン２００質量部、ｎ－ブチルメタクリレート３００質量部、γ－メタクリロキシプロピルトリメトキシシラン５００質量部、トリブチルホスフィンオキサイド（ＴＢＰＯ）４０質量部及びトルエン２００質量部からなる混合物を８時間かけて滴下した。滴下終了後、さらに、１１０℃に１５時間保持することで、不揮発分の化合物（Ｃ４－１）の４０質量％溶液を得た。 (Synthesis Example 1)
A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 800 parts by mass of toluene and 500 parts by mass of n-butanol, heated to 110 ° C. in a nitrogen atmosphere, and then 200 parts by mass of styrene. A mixture of 300 parts by mass of n-butyl methacrylate, 500 parts by mass of γ-methacryloxypropyltrimethoxysilane, 40 parts by mass of tributylphosphine oxide (TBPO) and 200 parts by mass of toluene was added dropwise over 8 hours. After completion of the dropping, the solution was further maintained at 110 ° C. for 15 hours to obtain a 40% by mass solution of the non-volatile compound (C4-1).
（実施例５）
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部、γ－グリシドキシプロピルトリメトキシシラン７質量部及びテトラエトキシシラン（以下、「ＴＥＯＳ」と略記する。）の部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（１）を得た。 (Example 5)
100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)), 7 parts by mass of γ-glycidoxypropyltrimethoxysilane and tetraethoxysilane (hereinafter referred to as “the polymer (A-1)”) 6 parts by mass of a partially hydrolyzed condensate (abbreviated as “TEOS”) (“ethyl silicate 40” manufactured by Colcoat Co., Ltd.) was uniformly mixed to obtain a paint (1).
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部、γ－グリシドキシプロピルトリメトキシシラン７質量部及びテトラエトキシシラン（以下、「ＴＥＯＳ」と略記する。）の部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（１）を得た。 (Example 5)
100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)), 7 parts by mass of γ-glycidoxypropyltrimethoxysilane and tetraethoxysilane (hereinafter referred to as “the polymer (A-1)”) 6 parts by mass of a partially hydrolyzed condensate (abbreviated as “TEOS”) (“ethyl silicate 40” manufactured by Colcoat Co., Ltd.) was uniformly mixed to obtain a paint (1).
［硬化塗膜の作製］
上記で得られた塗料（１）をトルエン／キシレン／ｎ－ブタノール／セロソルブアセテート＝４０／２０／３０／１０（質量比）からなる混合溶剤でスプレー塗装可能な粘度になるまで希釈した。次いで、基材としてガラス板（厚さ２ｍｍ）を用いて乾燥膜厚が約２０μｍとなるようにスプレー塗装した後、２３℃、５０％ＲＨの雰囲気下で７日間乾燥して硬化塗膜を得た。 [Preparation of cured coating film]
The paint (1) obtained above was diluted with a mixed solvent of toluene / xylene / n-butanol / cellosolve acetate = 40/20/30/10 (mass ratio) until the viscosity was sprayable. Next, after spray coating using a glass plate (thickness 2 mm) as a base material so that the dry film thickness is about 20 μm, it is dried for 7 days in an atmosphere of 23 ° C. and 50% RH to obtain a cured coating film. It was.
上記で得られた塗料（１）をトルエン／キシレン／ｎ－ブタノール／セロソルブアセテート＝４０／２０／３０／１０（質量比）からなる混合溶剤でスプレー塗装可能な粘度になるまで希釈した。次いで、基材としてガラス板（厚さ２ｍｍ）を用いて乾燥膜厚が約２０μｍとなるようにスプレー塗装した後、２３℃、５０％ＲＨの雰囲気下で７日間乾燥して硬化塗膜を得た。 [Preparation of cured coating film]
The paint (1) obtained above was diluted with a mixed solvent of toluene / xylene / n-butanol / cellosolve acetate = 40/20/30/10 (mass ratio) until the viscosity was sprayable. Next, after spray coating using a glass plate (thickness 2 mm) as a base material so that the dry film thickness is about 20 μm, it is dried for 7 days in an atmosphere of 23 ° C. and 50% RH to obtain a cured coating film. It was.
［鉛筆硬度の測定］
上記で得られた硬化塗膜について、ＪＩＳ試験方法 Ｋ５６００－５－４：１９９９に準拠して、鉛筆に三菱鉛筆株式会社製「ユニ」を用いて、鉛筆硬度を測定した。なお、鉛筆硬度の測定は、上記の硬化塗膜を有するガラス板のまま行った。 [Measurement of pencil hardness]
With respect to the cured coating film obtained above, the pencil hardness was measured using “Uni” manufactured by Mitsubishi Pencil Co., Ltd. as the pencil in accordance with JIS test method K5600-5-4: 1999. In addition, the measurement of pencil hardness was performed with the glass plate which has said cured coating film.
上記で得られた硬化塗膜について、ＪＩＳ試験方法 Ｋ５６００－５－４：１９９９に準拠して、鉛筆に三菱鉛筆株式会社製「ユニ」を用いて、鉛筆硬度を測定した。なお、鉛筆硬度の測定は、上記の硬化塗膜を有するガラス板のまま行った。 [Measurement of pencil hardness]
With respect to the cured coating film obtained above, the pencil hardness was measured using “Uni” manufactured by Mitsubishi Pencil Co., Ltd. as the pencil in accordance with JIS test method K5600-5-4: 1999. In addition, the measurement of pencil hardness was performed with the glass plate which has said cured coating film.
［硬化性の評価（ゲル分率の測定）］
上記の硬化塗膜の作製で基材として用いたガラス板に代えて、ポリプロピレン・シート（厚さ２ｍｍ）を用いた以外は同様に操作して、硬化塗膜を得た。得られた硬化塗膜を基材から剥がして、５０ｍｍ×５０ｍｍの大きさに切断して秤量した後、アセトンに浸漬し、１時間後又は２４時間後に取り出した。取り出した硬化塗膜を１０８℃で１時間乾燥し、再び秤量した。硬化塗膜のアセトン浸漬前後の質量から、下式に従ってゲル分率を計算し、硬化性を評価した。
ゲル分率（％）＝（浸漬後の硬化塗膜質量）／（浸漬前の硬化塗膜質量）×１００ [Evaluation of curability (measurement of gel fraction)]
A cured coating film was obtained in the same manner except that a polypropylene sheet (thickness 2 mm) was used instead of the glass plate used as the substrate in the preparation of the cured coating film. The obtained cured coating film was peeled off from the substrate, cut into a size of 50 mm × 50 mm, weighed, immersed in acetone, and taken out after 1 hour or 24 hours. The taken out cured coating film was dried at 108 ° C. for 1 hour and weighed again. From the mass before and after acetone immersion of the cured coating film, the gel fraction was calculated according to the following formula and the curability was evaluated.
Gel fraction (%) = (mass of cured coating film after immersion) / (mass of cured coating film before immersion) × 100
上記の硬化塗膜の作製で基材として用いたガラス板に代えて、ポリプロピレン・シート（厚さ２ｍｍ）を用いた以外は同様に操作して、硬化塗膜を得た。得られた硬化塗膜を基材から剥がして、５０ｍｍ×５０ｍｍの大きさに切断して秤量した後、アセトンに浸漬し、１時間後又は２４時間後に取り出した。取り出した硬化塗膜を１０８℃で１時間乾燥し、再び秤量した。硬化塗膜のアセトン浸漬前後の質量から、下式に従ってゲル分率を計算し、硬化性を評価した。
ゲル分率（％）＝（浸漬後の硬化塗膜質量）／（浸漬前の硬化塗膜質量）×１００ [Evaluation of curability (measurement of gel fraction)]
A cured coating film was obtained in the same manner except that a polypropylene sheet (thickness 2 mm) was used instead of the glass plate used as the substrate in the preparation of the cured coating film. The obtained cured coating film was peeled off from the substrate, cut into a size of 50 mm × 50 mm, weighed, immersed in acetone, and taken out after 1 hour or 24 hours. The taken out cured coating film was dried at 108 ° C. for 1 hour and weighed again. From the mass before and after acetone immersion of the cured coating film, the gel fraction was calculated according to the following formula and the curability was evaluated.
Gel fraction (%) = (mass of cured coating film after immersion) / (mass of cured coating film before immersion) × 100
（実施例６～８）
実施例１で用いた樹脂組成物（１）に代えて、実施例２～４で得られた樹脂組成物（２）～（４）（重合体（Ａ－２）～（Ａ－４）の５０質量％溶液）を用いた以外は実施例１と同様に操作して、塗料（２）～（４）を得た。得られた塗料を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Examples 6 to 8)
Instead of the resin composition (1) used in Example 1, the resin compositions (2) to (4) obtained in Examples 2 to 4 (polymers (A-2) to (A-4)) A paint (2) to (4) was obtained in the same manner as in Example 1 except that a 50% by mass solution) was used. Using the obtained coating material, production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
実施例１で用いた樹脂組成物（１）に代えて、実施例２～４で得られた樹脂組成物（２）～（４）（重合体（Ａ－２）～（Ａ－４）の５０質量％溶液）を用いた以外は実施例１と同様に操作して、塗料（２）～（４）を得た。得られた塗料を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Examples 6 to 8)
Instead of the resin composition (1) used in Example 1, the resin compositions (2) to (4) obtained in Examples 2 to 4 (polymers (A-2) to (A-4)) A paint (2) to (4) was obtained in the same manner as in Example 1 except that a 50% by mass solution) was used. Using the obtained coating material, production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
（実施例９）
実施例１で得られた塗料（１）に、硬化触媒としてジブチル錫ジオクテート０．５質量部を加えて、塗料（５）を得た。この塗料（５）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 Example 9
To the coating material (1) obtained in Example 1, 0.5 part by weight of dibutyltin dioctate was added as a curing catalyst to obtain a coating material (5). Using this paint (5), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
実施例１で得られた塗料（１）に、硬化触媒としてジブチル錫ジオクテート０．５質量部を加えて、塗料（５）を得た。この塗料（５）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 Example 9
To the coating material (1) obtained in Example 1, 0.5 part by weight of dibutyltin dioctate was added as a curing catalyst to obtain a coating material (5). Using this paint (5), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
（実施例１０）
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部、ポリエポキシ化合物（ナガセケムテックス株式会社製「デコナールＥＸ－４１１」）５．９質量部及びＴＥＯＳの部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（６）を得た。この塗料（６）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Example 10)
4. 100 parts by mass of resin composition (1) obtained in Example 1 (50% by mass solution of polymer (A-1)), polyepoxy compound (“Deconal EX-411” manufactured by Nagase ChemteX Corporation) 9 parts by mass and 6 parts by mass of TEOS partially hydrolyzed condensate (“Ecosilicate 40” manufactured by Colcoat Co., Ltd.) were uniformly mixed to obtain paint (6). Using this paint (6), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部、ポリエポキシ化合物（ナガセケムテックス株式会社製「デコナールＥＸ－４１１」）５．９質量部及びＴＥＯＳの部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（６）を得た。この塗料（６）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Example 10)
4. 100 parts by mass of resin composition (1) obtained in Example 1 (50% by mass solution of polymer (A-1)), polyepoxy compound (“Deconal EX-411” manufactured by Nagase ChemteX Corporation) 9 parts by mass and 6 parts by mass of TEOS partially hydrolyzed condensate (“Ecosilicate 40” manufactured by Colcoat Co., Ltd.) were uniformly mixed to obtain paint (6). Using this paint (6), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
（実施例１１）
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部及び合成例１で得られた化合物（Ｃ４－１）１００質量部を均一に混合して、塗料（７）を得た。この塗料（７）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Example 11)
100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)) and 100 parts by mass of the compound (C4-1) obtained in Synthesis Example 1 were uniformly added. By mixing, paint (7) was obtained. Using this paint (7), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
実施例１で得られた樹脂組成物（１）（重合体（Ａ－１）の５０質量％溶液）１００質量部及び合成例１で得られた化合物（Ｃ４－１）１００質量部を均一に混合して、塗料（７）を得た。この塗料（７）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Example 11)
100 parts by mass of the resin composition (1) obtained in Example 1 (50% by mass solution of the polymer (A-1)) and 100 parts by mass of the compound (C4-1) obtained in Synthesis Example 1 were uniformly added. By mixing, paint (7) was obtained. Using this paint (7), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
（比較例４）
比較例１で得られた樹脂組成物（５）（重合体（Ｒ－１）の５０質量％溶液）１００質量部、γ－グリシドキシプロピルトリメトキシシラン７質量部及びＴＥＯＳの部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（８）を得た。この塗料（８）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Comparative Example 4)
Partial hydrolytic condensation of 100 parts by weight of the resin composition (5) obtained in Comparative Example 1 (50% by weight solution of polymer (R-1)), 7 parts by weight of γ-glycidoxypropyltrimethoxysilane and TEOS 6 parts by mass of a product (“Ethyl silicate 40” manufactured by Colcoat Co., Ltd.) was uniformly mixed to obtain a paint (8). Using this paint (8), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
比較例１で得られた樹脂組成物（５）（重合体（Ｒ－１）の５０質量％溶液）１００質量部、γ－グリシドキシプロピルトリメトキシシラン７質量部及びＴＥＯＳの部分加水分解縮合物（コルコート株式会社製「エチルシリケート４０」）６質量部を均一に混合して、塗料（８）を得た。この塗料（８）を用いて、実施例１で行った硬化塗膜の作製、鉛筆硬度の測定及び硬化性の評価（ゲル分率の測定）を行った。 (Comparative Example 4)
Partial hydrolytic condensation of 100 parts by weight of the resin composition (5) obtained in Comparative Example 1 (50% by weight solution of polymer (R-1)), 7 parts by weight of γ-glycidoxypropyltrimethoxysilane and TEOS 6 parts by mass of a product (“Ethyl silicate 40” manufactured by Colcoat Co., Ltd.) was uniformly mixed to obtain a paint (8). Using this paint (8), production of the cured coating film performed in Example 1, measurement of pencil hardness, and evaluation of curability (measurement of gel fraction) were performed.
上記の実施例５～１１及び比較例４で得られた塗料（１）～（８）の組成及び評価結果を表２に示す。
Table 2 shows the compositions and evaluation results of the paints (1) to (8) obtained in Examples 5 to 11 and Comparative Example 4 above.
表２に示した結果から、本発明の塗料（１）～（７）は、その硬化塗膜の鉛筆硬度がＨであり、硬化塗膜の表面硬度が十分高いことが分かった。また、硬化塗膜形成後３時間の時点でのゲル分率は６０％以上であり、初期硬化性にも優れることが分かった。一方、比較例４は、前記一般式（Ｉ）で表される単量体（ａ１）を用いなかった重合体を含有する樹脂組成物を用いた塗料の例であるが、その硬化塗膜の鉛筆硬度はＨで本発明の塗料とほぼ差がない表面硬度を有するが、硬化塗膜形成後３時間の時点でのゲル分率は４７％と低く、初期硬化性に劣ることが分かった。
From the results shown in Table 2, it was found that in the paints (1) to (7) of the present invention, the pencil hardness of the cured coating film was H, and the surface hardness of the cured coating film was sufficiently high. Moreover, it turned out that the gel fraction in the time of 3 hours after cured coating film formation is 60% or more, and is excellent also in initial stage curability. On the other hand, Comparative Example 4 is an example of a paint using a resin composition containing a polymer not using the monomer (a1) represented by the general formula (I). The pencil hardness is H, which has a surface hardness that is not substantially different from that of the paint of the present invention, but the gel fraction at 3 hours after the formation of the cured coating film was as low as 47%, indicating that the initial curability was inferior.
Claims (6)
- 下記一般式（Ｉ）で表される単量体（ａ１）及びアミノ基を有する単量体（ａ２）を必須の単量体成分として重合した重合体（Ａ）と、アルコール（Ｂ）とを含有することを特徴とする樹脂組成物。
- 前記単量体（ａ２）が、Ｎ，Ｎ－ジアルキルアミノアルキルアクリレート、Ｎ，Ｎ－ジアルキルアミノアルキルメタクリレート、Ｎ，Ｎ－ジアルキルアミノアルキルアクリルアミド及びＮ，Ｎ－ジアルキルアミノアルキルメタクリルアミドからなる群から選ばれる少なくとも１種の単量体である請求項１記載の樹脂組成物。 The monomer (a2) is selected from the group consisting of N, N-dialkylaminoalkyl acrylate, N, N-dialkylaminoalkyl methacrylate, N, N-dialkylaminoalkyl acrylamide and N, N-dialkylaminoalkyl methacrylamide The resin composition according to claim 1, wherein the resin composition is at least one monomer.
- 前記アルコール（Ｂ）が、炭素原子数１～１０のアルコールである請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the alcohol (B) is an alcohol having 1 to 10 carbon atoms.
- 請求項１～３のいずれか１項記載の樹脂組成物と、エポキシ基、シラノール基及び加水分解性シリル基からなる群から選ばれる少なくとも１種の官能基を有する化合物を含む硬化剤（Ｃ）とを含有することを特徴とする塗料。 A curing agent (C) comprising the resin composition according to any one of claims 1 to 3 and a compound having at least one functional group selected from the group consisting of an epoxy group, a silanol group and a hydrolyzable silyl group. And a paint characterized by containing.
- 前記硬化剤（Ｃ）が、１分子中にエポキシ基及び加水分解性シリル基を有する化合物（Ｃ１）、ポリエポキシ化合物（Ｃ２）、及び前記化合物（Ｃ１）以外の加水分解性シリル基及び／又はシラノール基を有する化合物（Ｃ３）からなる群から選ばれる少なくとも１つを含むものである請求項４記載の塗料。 The curing agent (C) is a hydrolyzable silyl group other than the compound (C1), polyepoxy compound (C2), and compound (C1) having an epoxy group and a hydrolyzable silyl group in one molecule and / or 5. The paint according to claim 4, comprising at least one selected from the group consisting of a compound (C3) having a silanol group.
- 請求項４又は５記載の塗料によって塗装されたことを特徴とする物品。 An article coated with the paint according to claim 4 or 5.
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| JP2007302749A (en) * | 2006-05-09 | 2007-11-22 | Kaneka Corp | Curable composition |
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| JPS61225244A (en) * | 1985-03-30 | 1986-10-07 | Dainippon Ink & Chem Inc | Room temperature curing resin composition |
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