JP2019006873A - Curable resin composition, coating agent, and article - Google Patents

Abstract

To provide a curable resin composition that is excellent in storage stability and can form a coating film excellent in various kinds of physical properties such as heat resistance and the like even in a one-pack curing specification excellent in workability.SOLUTION: The curable resin composition comprises (A) a composite resin which has (a1) a polysiloxane having (U1) a structural unit represented by formula (1) or (2) and (U2) a structural unit represented by formula (3) and (a2) a polymer bonded through a linkage represented by formula (4) and which is dissolved or dispersed in a medium. Formula (1): -RSiO-; Formula (2): -RRSiO- (Ris an aromatic hydrocarbon substituent; and Ris an aromatic hydrocarbon substituent or an alkyl group); and Formula (3): -RSiO- (Ris a methyl group or an ethyl group).SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition that can be used in various applications including a coating agent.

  In recent years, highly functional materials that combine the characteristics of inorganic and organic materials have been widely developed in various industrial fields. Inorganic materials have excellent durability such as weather resistance, heat resistance, and scratch resistance. It is generally known that is rich in flexibility and workability. Under such circumstances, a curable resin composition in which an inorganic material and an organic material are combined has been proposed (see, for example, Patent Document 1). The coating film of this resin curable composition has high weather resistance, but when higher heat resistance is required, it is essential to use a curing agent, which is inferior in coating workability. Was pointed out.

  Therefore, there has been a demand for a material that can form a coating film excellent in heat resistance with a one-component curing specification excellent in workability.

Japanese Patent No. 3521431

  The problem to be solved by the present invention is a curable resin composition capable of forming a coating film excellent in various physical properties such as heat resistance even in a one-component curing specification excellent in storage stability and workability, and the curing It is providing the articles | goods which have the coating agent using an adhesive resin composition, and the coating film of this coating agent.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a curable resin composition in which a composite resin in which a specific polysiloxane and a specific polymer segment are bonded is dissolved or dispersed in a medium, The present invention has been completed by finding that a coating film excellent in various physical properties such as heat resistance can be formed even in a one-component curing specification having excellent storage stability and workability.

  That is, the present invention relates to a polysiloxane (a1) and a polymer having the structural unit (U1) represented by the general formula (1) or (2) and the structural unit (U2) represented by the general formula (3). (A2) is a curable resin composition in which the composite resin (A) bonded with the bond represented by the general formula (4) is dissolved or dispersed in a medium, and the composite resin (A) The polysiloxane (a1) is 75 to 99% by mass, and the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

（一般式（１）、（２）中のＲ^１は芳香族炭化水素置換基を表し、Ｒ^２は芳香族炭化水素置換基又はアルキル基を表す。）

(R ¹ in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R ² represents an aromatic hydrocarbon substituent or an alkyl group.)

（一般式（３）中のＲ^３はメチル基又はエチル基を表す。）

(R ³ in the general formula (3) represents a methyl group or an ethyl group.)

  Since the curable resin composition of the present invention can form a coating film excellent in substrate adhesion, heat resistance, weather resistance, etc., a coating agent for forming a primer layer or a coating agent for forming a topcoat layer on various substrates, etc. Can be suitably used.

  The curable resin composition of the present invention includes a polysiloxane (a1) having a structural unit (U1) represented by the general formula (1) or (2) and a structural unit (U2) represented by the general formula (3). ) And the polymer (a2) are bonded to each other by a bond represented by the general formula (4), and the composite resin (A) is dissolved or dispersed in a medium, the composite resin The said polysiloxane (a1) in (A) is 75-99 mass%, and the said structural unit (U1) in the said polysiloxane (a1) is 10-55 mass%.

  First, the composite resin (A) will be described. The composite resin (A) is obtained by bonding the polysiloxane (a1) and the polymer (a2) by a bond represented by the general formula (4).

  Examples of the form of the composite resin (A) include a composite resin having a graft structure in which the polysiloxane (a1) is chemically bonded as a side chain of the polymer (a2), and the polymer (a2). Examples thereof include composite resins having a block structure in which the polysiloxane (a1) is chemically bonded.

  The bond represented by the general formula (4) includes a silanol group and / or hydrolyzable silyl group of the polysiloxane (a1), and a silanol group and / or hydrolyzable silyl group of the polymer (a2). This is caused by a dehydration condensation reaction with a group. Therefore, in the general formula (4), carbon atoms constitute a part of the polymer (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane (a1).

  Although it is important that the polysiloxane (a1) in the composite resin (A) is 75 to 99% by mass, a coating film having excellent storage stability and more excellent heat resistance and weather resistance can be obtained. Therefore, it is preferable that it is 80-98 mass%, and it is more preferable that it is 85-95 mass%.

  In addition, the mass ratio of the polysiloxane (a1) is based on the charged ratio of the raw materials used for the production of the composite resin (A), and generates by-products such as methanol and ethanol that can be generated by hydrolysis condensation reaction. This is a value calculated in consideration.

  The polysiloxane (a1) has a chain structure composed of silicon atoms and oxygen atoms, and has a hydrolyzable silyl group and / or a silanol group.

  The hydrolyzable silyl group is an atomic group in which the hydrolyzable group is directly bonded to the silicon atom, and has, for example, a structure represented by the following general formula (5).

（式中、Ｒ^４はアルキル基、アリール基またはアラルキル基等の１価の有機基を、Ｒ^５はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基である。また、ｎは０〜２の整数である。）

Wherein R ⁴ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, and R ⁵ is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group, amide A group, an aminooxy group, an iminooxy group or an alkenyloxy group, and n is an integer of 0 to 2.)

  The hydrolyzable group is capable of forming a hydroxyl group under the influence of water. For example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group Group, iminooxy group, alkenyloxy group and the like, among which an alkoxy group and a substituted alkoxy group are preferable.

  The silanol group represents an atomic group in which a hydroxyl group is directly bonded to the silicon atom, and is formed when the hydrolyzable silyl group is hydrolyzed.

  It is important that the polysiloxane (a1) has 10 to 55% by mass of the structural unit (U1) represented by the general formula (1) or (2) from the viewpoints of storage stability and physical properties of the coating film. However, since the coating film which is more excellent in heat resistance and a weather resistance is obtained, it is more preferable to have 10-40 mass%.

  Moreover, it is important that the polysiloxane (a1) has 10% by mass or more of the structural unit (U2) represented by the general formula (3) from the viewpoint of the weather resistance of the coating film, and 15% by mass or more. It is preferable to have.

  The polysiloxane (a1) includes, for example, a structural unit (U3) represented by the following general formula (6) or (7) as a structural unit other than the structural unit (U1) and the structural unit (U2). Can have.

（一般式（６）、（７）中のＲ^６は芳香族炭化水素置換基以外の炭素原子数が３〜１２の有機基を表し、Ｒ^７及びＲ^８はそれぞれ独立してメチル基又はエチル基を表す。）

(R ⁶ in the general formulas (6) and (7) represents an organic group having 3 to 12 carbon atoms other than the aromatic hydrocarbon substituent, and R ⁷ and R ⁸ are each independently a methyl group or an ethyl group. Represents a group.)

  As said polysiloxane (a1), what is obtained by hydrolyzing and condensing the silane compound mentioned later completely or partially can be used, for example.

  The structural unit (U1) of the polysiloxane (a1) has an aromatic ring such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, phenyltrichlorosilane, and diphenyldichlorosilane. By using a silane compound or a partially hydrolyzed condensate thereof, it can be easily introduced into the polysiloxane (a1), but among these, the storage stability is further improved and the resulting coating is obtained. Since the appearance, adhesion, and heat resistance of the film are further improved, it is preferable to use phenyltrimethoxysilane or diphenyldimethoxysilane.

  The structural unit (U2) is, for example, a silane compound such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrichlorosilane, and ethyltrichlorosilane. Alternatively, they can be easily introduced into the polysiloxane (a1) by using a partially hydrolyzed condensate thereof.

  The structural unit (U3) includes, for example, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane, vinyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane, Easily introduced into the polysiloxane (a1) by using silane compounds such as dimethyldichlorosilane and diethyldichlorosilane, and partial hydrolysis condensates thereof. Rukoto can.

  These silane compounds may be used alone or in combination of two or more.

  The polymer (a2) has a hydrolyzable silyl group and / or silanol group that can react with the polysiloxane (a1).

  As said polymer (a2), since the coating-film physical properties, such as heat resistance of a coating film obtained and a weather resistance, improve more, using what has a number average molecular weight of 3,000-100,000 is used. Preferably, those having a number average molecular weight of 5,000 to 25,000 are more preferably used. Here, the number average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement.

  Examples of the polymer (a2) include vinyl polymers such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers, and aromatic vinyl polymers; polyester resins, alkyd resins, polyurethane resins, and the like. A vinyl polymer is preferable because of excellent storage stability and excellent appearance and adhesion of the resulting coating film.

  As the vinyl polymer, for example, a polymer produced by polymerizing various vinyl monomers in the presence of a polymerization initiator in an organic solvent can be used.

  The hydrolyzable silyl group can be easily introduced into the vinyl polymer, for example, by polymerizing a vinyl monomer having a hydrolyzable silyl group.

  Examples of the vinyl monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meta ) Acryloyloxypropylmethyldimethoxysilane and the like can be used, and among them, 3- (meth) acryloyloxypropyltrimethoxysilane is preferably used.

  Examples of the raw material for the vinyl polymer other than the vinyl monomer having a hydrolyzable silyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meta ) (Meth) acrylic acid ester compounds such as acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) ) Vinyl monomers having a hydroxyl group such as acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, glycerol mono (meth) acrylate; methoxypolyethylene Glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polyethylene glycol-polypropylene glycol (meth) acrylate phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate Vinyl monomers having a polyoxyalkylene group whose ends are blocked with alkoxy groups or phenoxy groups; vinyl monomers having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate; N -Vinyl monomer having a secondary amino group such as methylaminoethyl (meth) acrylate; Vinyl monomer having a primary amino group such as aminomethyl acrylate Vinyl monomers having a group having a basic nitrogen atom such as; vinyl monomers having a fluorine atom such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl ester compounds such as vinyl acetate; methyl vinyl ether Vinyl ether compounds such as: nitrile compounds of unsaturated carboxylic acids such as (meth) acrylonitrile; vinyl compounds having an aromatic ring such as styrene; α-olefin compounds such as isoprene; vinyl having an epoxy group such as glycidyl (meth) acrylate Monomer; Vinyl monomer having an amide group such as (meth) acrylamide; Vinyl monomer having a methylolamide group such as N-methylol (meth) acrylamide and an alkoxy product thereof; 2-aziridinylethyl (meta ) Vinyl monomers having an aziridinyl group such as acrylate; A) Vinyl monomers having isocyanate groups such as acryloyl isocyanate and / or blocked isocyanate groups; vinyl monomers having oxazoline groups such as 2-isopropenyl-2-oxazoline; dicyclopentenyl (meth) Vinyl monomers having a cyclopentenyl group such as acrylate; vinyl monomers having a carbonyl group such as acrolein; vinyl monomers having an acetoacetyl group such as acetoacetoxyethyl (meth) acrylate; (meth) acrylic acid, A monomer having a carboxyl group such as itaconic acid, maleic acid, or a half ester thereof, or a salt thereof can be used.

  Examples of the organic solvent that can be used for producing the vinyl polymer include aliphatic or alicyclic hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, cyclopentane, and cyclooctane; toluene, xylene Or an aromatic hydrocarbon compound such as ethylbenzene; ester compounds such as ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-amyl alcohol, i-amyl alcohol, tert-amyl alcohol, ethylene Alcohol compounds such as recall monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone; dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n -Ether compounds such as butyl ether; Chlorinated hydrocarbon compounds such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane, tetrachloroethane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, and the like can be used. These organic solvents may be used alone or in combination of two or more.

  Examples of the polymerization initiator that can be used for producing the vinyl polymer include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4′-azobis (4-cyano). An azo initiator such as valeric acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the persulfate that is a representative of the polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Specific examples of the organic peroxide include benzoyl peroxide. , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxyesters such as laurate and t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, and t-butyl hydroperoxide can be used.

  The polymerization initiator may be used in an amount that allows the polymerization to proceed smoothly, but should be 10% by mass or less based on the total amount of vinyl monomers used in the production of the vinyl polymer (a2). Is preferred.

The glass transition temperature of the vinyl polymer is preferably in the range of −50 to 90 ° C. because the coating film properties such as heat resistance and weather resistance of the coating film obtained are further improved. In the present invention, the glass transition temperature (Tg) refers to a glass transition temperature calculated by the following FOX equation.
Formula of FOX: 1 / Tg = W1 / Tg1 + W2 / Tg2 +
(Tg: glass transition temperature to be obtained, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1)

  Moreover, it is preferable to form the said polysiloxane (a1) by passing through a two-step reaction process in the process of manufacturing the said composite resin (A). Specifically, a polysiloxane structure is formed by reacting a hydrolyzable group or the like of the vinyl polymer (a1) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction. By reacting a product with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane, a structure composed of polysiloxane (a1) can be formed. Thereby, the curable resin composition which can form the coating film excellent in durability, such as heat resistance and a weather resistance, can be obtained further.

  The composite resin (A) can be produced, for example, by the following steps (I) to (II).

  The step (I) is a step of obtaining an organic solvent solution of the vinyl polymer (a2) by polymerizing the above vinyl monomer in the presence of the polymerization initiator in an organic solvent.

  Such a polymerization reaction is performed, for example, by sequentially or collectively supplying the vinyl monomer in an organic solvent containing a polymerization initiator, and then stirring at a temperature of 20 to 120 ° C. for about 0.5 to 24 hours. It is preferable.

  In the step (II), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a2) and a hydrolysis possessed by the silane compound under an organic solvent solution of the vinyl polymer (a2). The composite resin (A) in which the vinyl polymer (a2) and the polysiloxane (a1) are bonded to each other by advancing a reaction with a functional silyl group or a silanol group and a hydrolysis condensation reaction between the silane compounds. ) To obtain an organic solvent solution.

  In this reaction, for example, following the step (I), the silane compound capable of forming the polysiloxane (a1) is sequentially supplied or collectively supplied into the organic solvent solution of the vinyl polymer (a2), and then Under stirring, it is preferably performed in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  The step (II) preferably further undergoes a two-step reaction step. Specifically, a step of reacting the hydrolyzable silyl group or silanol group of the vinyl polymer (a2) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction product And a step of reacting a methyltrialkoxysilane such as methyltrimethoxysilane or ethyltrimethoxysilane and a condensate obtained by condensing ethyltrialkoxysilane in advance. By performing the polysiloxane (a1) structure formation in the above two steps, a curable resin composition capable of forming a coating film having excellent durability such as heat resistance and weather resistance can be obtained. .

  The curable resin composition of the present invention is one in which the composite resin (A) is dissolved or dispersed in a medium. The medium can be used, for example, when producing the vinyl polymer. And various organic solvents listed as examples.

  The curable resin composition of the present invention can contain a thermosetting resin as necessary. Examples of such thermosetting resins include vinyl resins, polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, or modified resins thereof.

  In the curable resin composition of the present invention, various inorganic particles such as clay mineral, metal, metal oxide, and glass can be used as necessary. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

  The curable resin composition of the present invention includes a photocatalytic compound, inorganic pigment, organic pigment, extender pigment, wax, surfactant, stabilizer, flow regulator, dye, leveling agent, rheology control agent, if necessary. Various additives such as an ultraviolet absorber, an antioxidant, and a plasticizer can be used.

  Since the curable resin composition of the present invention is excellent in storage stability, it can be used for various applications such as a coating agent and an adhesive. Especially, since the curable resin composition of this invention can form the coating film excellent in heat resistance and a weather resistance, it is preferable to use it for a coating agent, the coating agent for top layer formation, and the coating agent for primer layer formation It is more preferable to use it.

  As a base material which can apply | coat the said coating agent and can form a coating film, an inorganic base material, a metal base material, a plastic base material, a glass base material, paper, a wood base material, a fiber base material etc. are mentioned, for example.

  The coating agent of the present invention forms, for example, a coating film excellent in appearance, durability, weather resistance and the like after the exposure test by directly applying the coating agent to the surface of the substrate, followed by drying and curing. can do.

  A coated product can be obtained by applying and curing the coating agent on various substrates as described above. At that time, (1) the coating agent is directly applied to the substrate, (2) the primer coating is applied on the substrate in advance, and then the coating agent is applied as the top coating. (3) the substrate A coated product can be obtained by a coating method such as applying the coating agent as a base coat and then applying another top coat to form a coating film.

  Examples of the method for applying the coating agent of the present invention include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, and electrodeposition coating.

  Moreover, when obtaining the coating material which has the coating film which consists of the said coating agent with the coating method of said (2) or (3), conventionally known acrylic resin-type paint and polyester resin as undercoat paint and topcoat paint Paints, alkyd resin paints, epoxy resin paints, fatty acid-modified epoxy resin paints, silicone resin paints, polyurethane resin paints, and the like can be used.

  The method for drying and curing may be a method of curing for about 1 to 10 days at room temperature. From the viewpoint of rapidly curing, the temperature is 50 to 250 ° C. for 1 to 600 seconds. A method of heating to a certain extent is preferred. Moreover, when using the plastic base material which deform | transforms and discolors easily at comparatively high temperature, it is preferable to perform curing at comparatively low temperature of about 30-100 degreeC.

  The film thickness of the coating film formed using the coating agent of the present invention can be set to 0.5 to 1,000 μm depending on the use of the substrate.

  As an article having a coating film formed by using the coating agent of the present invention by the method as described above, for example, interior / exterior materials of buildings such as outer walls, roofs, glass, decorative boards; soundproof walls, drainage grooves Civil engineering materials such as: Housings for home appliances such as TVs, refrigerators, washing machines, and air conditioners; Housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines; Housings for OA devices such as printers and facsimiles Body: Interior and exterior materials of various vehicles such as automobiles and railway vehicles; industrial machinery and the like.

  Next, the present invention will be specifically described with reference to examples and comparative examples. The average molecular weight of the resin is measured under the following GPC measurement conditions.

[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.

(Monodispersed polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

(Synthesis Example 1: Synthesis of condensate (a1′-1) of methyltrimethoxysilane)
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen gas inlet, 1,421 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as “MTMS”) was charged, and the temperature was raised to 60 ° C. Warm up. Next, a mixture of 0.17 parts by mass of iso-propyl acid phosphate (“Phoslex A-3” manufactured by SC Organic Chemical Co., Ltd.) and 207 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes. The mixture was stirred at a temperature of 4 ° C. for 4 hours to cause hydrolysis and condensation reaction.
The condensate obtained by the above hydrolysis condensation reaction is subjected to a temperature of 40 to 60 ° C. and a reduced pressure of 40 to 1.3 kPa (the reduced pressure condition at the start of the distillation of methanol is 40 kPa, and finally becomes 1.3 kPa) (Hereinafter the same shall apply)), and the methanol and water produced in the reaction process are removed to contain the MTMS condensate (a1′-1) having a number average molecular weight of 1,000. 1,000 parts by weight of a liquid (70% by mass of active ingredient) was obtained.
The effective component is a value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of silane monomers such as MTMS undergo a condensation reaction by the actual yield (parts by mass) after the condensation reaction [the methoxy of the silane monomer. The theoretical yield when all the groups undergo a condensation reaction (parts by mass) / the actual yield after the condensation reaction (parts by mass)] is calculated.

(Example 1: Production of curable resin composition (1))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 150 parts by mass of n-butanol (hereinafter abbreviated as “BuOH”), phenyltrimethoxysilane (hereinafter “PTMS”). 88 parts by mass and 233 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as “DMDMS”) were charged and the temperature was raised to 80 ° C.
Next, 84 parts by mass of methyl methacrylate (hereinafter abbreviated as “MMA”), 16 parts by mass of butyl methacrylate (hereinafter abbreviated as “BMA”), and butyl acrylate (hereinafter abbreviated as “BA”) at the same temperature. .) 13 parts by mass, 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as “MPTS”), 7 parts by mass, 12 parts by mass of BuOH, and tert-butylperoxy-2-ethylhexanoate (hereinafter, “TBPEH”) The mixture containing 2.4 parts by mass of the mixture was dropped into the reaction vessel over 4 hours, and after completion of the addition, the mixture was further reacted at the same temperature for 20 hours to have a number average having a hydrolyzable silyl group. An organic solvent solution of a vinyl polymer (a2-1) having a molecular weight of 10,200 was obtained.
Then, a mixture of 0.04 parts by mass of iso-propyl acid phosphate (“Phoslex A-3” manufactured by SC Organic Chemical Co., Ltd., hereinafter abbreviated as “A-3”) and 94 parts by mass of deionized water is added to 5 parts. The mixture was added dropwise for 1 minute, and further stirred at the same temperature for 10 hours to cause a hydrolytic condensation reaction, so that the hydrolyzable silyl group possessed by the vinyl polymer (a2-1) and the hydrolyzate possessed by the polysiloxane derived from PTMS and DMDMS were obtained. A liquid containing a composite resin in which a decomposable silyl group and a silanol group were bonded was obtained.
Subsequently, 398 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 67 parts by mass of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The product was distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, then 250 parts by weight of BuOH was added, and a curable resin composition (1 ) Was obtained at 1,000 parts by mass.

(Example 2: Production of curable resin composition (2))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 150 parts by mass of BuOH, 99 parts by mass of PTMS, and 263 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 5 hours. The solution was added dropwise, and after completion of the addition, the reaction was further carried out at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (a2-2) having a hydrolyzable silyl group and a number average molecular weight of 10,300.
Next, a mixture of 0.04 part by mass of A-3 and 106 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 -2) and a liquid containing a composite resin in which the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined.
Next, 447 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 76 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. Methanol and water produced by distillation of the product under the same conditions as in Synthesis Example 1 were removed, 250 parts by weight of BuOH was added, and a curable resin composition (2% with a nonvolatile content of 60.0% by weight) was added. ) Was obtained at 1,000 parts by mass.

(Example 3: Production of curable resin composition (3))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 105 parts by mass of PTMS, and 277 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 21 parts by mass of MMA, 4 parts by mass of BMA, 3 parts by mass of BA, 2 parts by mass of MPTS, 3 parts by mass of BuOH and 0.6 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 6 hours. After dropping, the reaction was further continued at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (a2-3) having a hydrolyzable silyl group and a number average molecular weight of 10,000.
Next, a mixture of 0.04 parts by mass of A-3 and 112 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 -3) and a liquid containing a composite resin in which the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined.
Next, 472 parts by weight of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 80 parts by weight of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. Methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The volatile resin composition (3% of non-volatile content is 60.1 mass%) ) Was obtained at 1,000 parts by mass.

(Example 4: Production of curable resin composition (4))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 108 parts by mass of PTMS, and 286 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 8 parts by mass of MMA, 2 parts by mass of BMA, 1 part by mass of BA, 1 part by mass of MPTS, 2 parts by mass of BuOH and 0.3 part by mass of TBPEH at the same temperature was added into the reaction vessel in 6 hours. The solution was added dropwise, and after completion of the addition, the reaction was further carried out at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (a2-4) having a hydrolyzable silyl group and a number average molecular weight of 10,300.
Next, a mixture of 0.05 part by mass of A-3 and 115 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 -4) and a liquid containing a composite resin in which the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined.
Next, 487 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 82 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The product was distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by weight of BuOH was added, and a curable resin composition (4%) with a nonvolatile content of 60.2% by weight was added. ) Was obtained at 1,000 parts by mass.

(Example 5: Production of curable resin composition (5))
Instead of the mixture containing 42 parts by weight of MMA, 8 parts by weight of BMA, 7 parts by weight of BA, 4 parts by weight of MPTS, 6 parts by weight of BuOH and 1.2 parts by weight of TBPEH used in Example 2, 18 parts by weight of MMA , 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of acrylic acid (hereinafter abbreviated as “AA”), 2 parts by mass of MPTS, 6 parts by mass of BuOH, and 0.9 part by mass of TBPEH are used. Except for this, the same operation as in Example 2 was performed to obtain 1,000 parts by mass of a curable resin composition (5) having a nonvolatile content of 60.0%.

(Example 6: Production of curable resin composition (6))
Instead of the mixture containing 42 parts by weight of MMA, 8 parts by weight of BMA, 7 parts by weight of BA, 4 parts by weight of MPTS, 6 parts by weight of BuOH and 1.2 parts by weight of TBPEH used in Example 2, 12 parts by weight of MMA , Except that a mixture containing 15 parts by mass of cyclohexyl methacrylate, 32 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of MPTS, 6 parts by mass of BuOH and 0.6 part by mass of TBPEH was used. 1,000 parts by mass of a curable resin composition (6) having a nonvolatile content of 60.2% was obtained.

(Example 7: Production of curable resin composition (7))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 133 parts by mass of diphenyldimethoxysilane (hereinafter abbreviated as “DPDMS”), and 350 parts by mass of DMDMS are added. The temperature was raised to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 part by mass of TBPEH at the same temperature was added to the reaction vessel. The solution was added dropwise in 5 hours, and after completion of the addition, the mixture was further reacted at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-7) having a hydrolyzable silyl group and a number average molecular weight of 20,000. It was.
Next, a mixture of 0.05 part by mass of A-3 and 134 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 The liquid containing the composite resin which the hydrolyzable silyl group which -7) has, and the hydrolyzable silyl group and silanol group which the polysiloxane derived from said DPDMS and DMDMS have couple | bonded was obtained.
Next, 309 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 52 parts by mass of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 15 hours to cause a hydrolysis and condensation reaction. Methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The curable resin composition (7% of a non volatile matter is 60.0 mass%) ) Was obtained at 1,000 parts by mass.

(Example 8: Production of curable resin composition (8))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 249 parts by mass of PTMS, and 263 parts by mass of DMDMS were charged and heated to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 part by mass of TBPEH at the same temperature was added to the reaction vessel. The solution was added dropwise in 5 hours, and after completion of the addition, the mixture was further reacted at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-8) having a hydrolyzable silyl group and a number average molecular weight of 20,100. It was.
Next, a mixture of 0.05 part by mass of A-3 and 147 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 A liquid containing a composite resin in which the hydrolyzable silyl group possessed by -8) and the hydrolyzable silyl group and silanol group possessed by the polysiloxane derived from PTMS and DMDMS were combined was obtained.
Next, 76 parts by mass of 3-glycidoxypropyltrimethoxysilane, 231 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1, and 56 parts by mass of deionized water were added to this solution. Methanol and water produced by distillation under the same conditions as in Synthesis Example 1 were removed by stirring for 15 hours at a temperature to remove methanol and water, and then 250 parts by mass of BuOH was added. 1,000 mass parts of 60.0 mass% curable resin composition (8) were obtained.

(Example 9: Production of curable resin composition (9))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 414 parts by mass of PTMS and 263 parts by mass of DMDMS were charged and heated to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 part by mass of TBPEH at the same temperature was added to the reaction vessel. The solution was added dropwise in 6 hours, and after completion of the addition, the mixture was further reacted at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-9) having a hydrolyzable silyl group and a number average molecular weight of 19,600. It was.
Next, a mixture of 0.07 parts by mass of A-3 and 192 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 The liquid containing the composite resin which the hydrolyzable silyl group which -9) has, and the hydrolyzable silyl group and silanol group which the polysiloxane derived from said PTMS and DMDMS have couple | bonded was obtained.
Next, 154 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 26 parts by mass of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 5 hours to cause a hydrolysis and condensation reaction. Methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, Non-volatile content is 60.1 mass% curable resin composition (9 ) Was obtained at 1,000 parts by mass.

(Comparative Example 1: Production of curable resin composition (R-1))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 33 parts by mass of PTMS, and 88 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 294 parts by mass of MMA, 55 parts by mass of BMA, 46 parts by mass of BA, 25 parts by mass of MPTS, 42 parts by mass of BuOH and 8.4 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 3 hours. After the dropwise addition, the reaction was further continued at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (Ra2-1) having a hydrolyzable silyl group and a number average molecular weight of 11,000.
Next, a mixture of 0.01 part by mass of A-3 and 35 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (Ra2 A liquid containing a composite resin in which the hydrolyzable silyl group possessed by -1) and the hydrolyzable silyl group and silanol group possessed by the polysiloxane derived from PTMS and DMDMS were obtained.
Next, 149 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 25 parts by mass of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The curable resin composition (R) whose non volatile matter is 60.0 mass% 1,000 parts by weight of -1) was obtained.

(Comparative Example 2: Production of curable resin composition (R-2))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 150 parts by mass of BuOH, 66 parts by mass of PTMS, and 175 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 168 parts by mass of MMA, 31 parts by mass of BMA, 26 parts by mass of BA, 14 parts by mass of MPTS, 24 parts by mass of BuOH and 4.8 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 4 hours. The solution was added dropwise, and after completion of the addition, the reaction was further carried out at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (Ra2-2) having a hydrolyzable silyl group and a number average molecular weight of 10,200.
Next, a mixture of 0.03 parts by mass of A-3 and 70 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (Ra2 -2) and a liquid containing a composite resin in which the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined.
Next, 298 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 50 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The curable resin composition (R) whose non volatile matter is 60.0 mass% -2) of 1,000 parts by mass was obtained.

(Comparative Example 3: Production of curable resin composition (R-3))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 111 parts by mass of PTMS, and 292 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, at the same temperature, a mixture of 0.05 part by mass of A-3 and 118 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction. And a liquid containing DMDMS-derived polysiloxane was obtained.
Next, 497 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 84 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The curable resin composition (R) whose non volatile matter is 60.0 mass% -3) 1,000 parts by mass of solution was obtained.

(Comparative Example 4: Production of curable resin composition (R-4))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 41 parts by mass of PTMS, and 263 parts by mass of DMDMS were charged and heated to 80 ° C.
Next, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 5 hours. The solution was added dropwise, and after completion of the addition, the reaction was further carried out at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (Ra2-4) having a hydrolyzable silyl group and a number average molecular weight of 10,400.
Subsequently, a mixture of 0.04 parts by mass of A-3 and 90 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction, whereby a vinyl polymer (Ra2 -4) and a liquid containing a composite resin in which the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined.
Subsequently, 501 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 85 parts by mass of deionized water were added to this liquid, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis and condensation reaction. The methanol and water produced | generated by distilling a thing on the conditions similar to the synthesis example 1 are removed, Then, 250 mass parts of BuOH is added, The curable resin composition (R) whose non volatile matter is 60.0 mass% -4) 1,000 parts by mass of solution was obtained.

(Comparative Example 5: Production of curable resin composition (R-5))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 150 parts by mass of BuOH, 332 parts by mass of PTMS, and 350 parts by mass of DMDMS were charged and heated to 80 ° C.
Subsequently, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 6 hours. The solution was added dropwise, and after completion of the addition, the mixture was further reacted at the same temperature for 20 hours to obtain an organic solvent solution of a vinyl polymer (Ra2-5) having a hydrolyzable silyl group and a number average molecular weight of 10,000.
Next, a mixture of 0.07 part by mass of A-3 and 195 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (Ra2 The liquid containing the composite resin which the hydrolyzable silyl group which -5) has, and the hydrolyzable silyl group and silanol group which the polysiloxane derived from said PTMS and DMDMS have couple | bonded was obtained.
Next, 153 parts by mass of 3-glycidoxypropyltrimethoxysilane and 35 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to undergo a hydrolysis and condensation reaction, as in Synthesis Example 1. The methanol and water produced | generated by distilling on the conditions of this are removed, 250 mass parts of BuOH is then added, and the solution 1000 of curable resin composition (R-5) whose non volatile matter is 60.0 mass% A mass part was obtained.

(Comparative Example 6: Production of curable resin composition (R-6))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 690 parts by weight of BuOH was charged and heated to 80 ° C.
Next, a mixture containing 193 parts by mass of MMA, 36 parts by mass of BMA, 30 parts by mass of BA, 17 parts by mass of MPTS, 28 parts by mass of BuOH and 5.5 parts by mass of TBPEH at the same temperature was added into the reaction vessel in 3 hours. After dropping, the reaction was further continued at the same temperature for 20 hours to obtain an organic solvent solution of vinyl polymer (Ra2-6) having a number average molecular weight of 10,300.
Next, 808 parts by mass of the curable resin composition (R-3) obtained in Comparative Example 3 and 192 parts by mass of an organic solvent solution of a vinyl polymer (Ra2-6) having a nonvolatile content of 28.0% by mass were mixed. By stirring at the same temperature for 1 hour, 1,000 parts by mass of a solution of a curable resin composition (R-6) having a nonvolatile content of 53.8% by mass was obtained.

[Evaluation of storage stability]
The storage stability of the curable resin composition obtained above was evaluated based on the viscosity ratio of the one stored for 30 days at 50 ° C. as the numerator and the initial viscosity as the denominator. The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The sample was stored by placing the obtained curable resin composition in a glass tube and allowing it to stand at 50 ° C. for 30 days. The closer this viscosity ratio is to 1, the better the storage stability, and the more excellent the storage stability with a viscosity ratio of 0.9 to 1.1. It was judged that there was.

[Production of cured coating film for evaluation]
The curable resin composition obtained above was coated on a soft glass plate, a chromate-treated aluminum plate manufactured by Engineering Test Service Co., Ltd. so that the thickness of the cured coating film was 30 μm, and The cured coating film for evaluation was obtained by drying in an environment for 1 week.

[Evaluation of coating appearance]
The cured coating film obtained above was observed visually, and the coating film appearance was evaluated according to the following criteria.
○: Cracks and whitening are not observed.
Δ: Some cracks or whitening is observed.
X: Generation | occurrence | production of a crack or whitening is recognized.

[Evaluation of adhesion]
The cured coating film for evaluation obtained above was measured based on the JIS K-5600 cross cut test method. A 1 mm wide cut is made on the cured coating film with a cutter, the number of grids is 100, cellophane tape is applied so as to cover all grids, and they are peeled off quickly to adhere and remain. Was counted and evaluated according to the following criteria.
○: No peeling.
Δ: The area of peeling is 1 to 64% of the total grid area.
X: The area of peeling is 65% or more of the total grid area.

[Evaluation of heat resistance (appearance)]
About the cured coating film for evaluation obtained above, after leaving still for 24 hours in a dryer at 300 ° C. atmosphere, the appearance after taking out from the dryer was visually observed and evaluated according to the following criteria.
○: Generation of cracks is not recognized.
Δ: Some cracks are observed.
X: Generation | occurrence | production of a crack is recognized.

[Evaluation of heat resistance (adhesion)]
The cured coating film for evaluation obtained above was left in a dryer at 300 ° C. for 24 hours, then taken out from the dryer and allowed to stand for 1 hour. After that, a 1mm wide cut is made on the coating film with a cutter, the number of grids is 100, cellophane tape is applied so as to cover all grids, and they are peeled off quickly and adhered to the grids. Was counted and evaluated according to the following criteria.
○: No peeling.
Δ: The area of peeling is 1 to 64% of the total grid area.
X: The area of peeling is 65% or more of the total grid area.

[Evaluation of solvent resistance]
About the cured coating film for evaluation obtained above, the state of the cured coating film after rubbing 50 times on the cured coating film with a felt soaked with ethanol was determined by touch and visual observation, and the following: Evaluation based on the criteria.
○: Softening and gloss reduction are not recognized.
(Triangle | delta): Some softening or gloss reduction is recognized.
X: Significant softening or gloss reduction is observed.

[Evaluation of acid resistance]
About the cured coating film for evaluation obtained above, a part of the cured coating film was immersed in a 5% sulfuric acid aqueous solution and allowed to stand at 25 ° C. for 7 days, and then the cured coating film was washed with water and dried. The surface condition was visually observed and evaluated according to the following criteria.
○: Etching traces are observed Δ: Some etching traces are observed.
*: Etching is recognized remarkably.

[Evaluation of weather resistance (appearance)]
About the cured coating film for evaluation obtained above, Dew panel optical weather meter (manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 70 ° C .; wet: 90% humidity, 50 ° C., light irradiation / Wet cycle = 8 hours / 4 hours), the coating film after 1,000 hours exposure was visually observed, and the coating film appearance was evaluated according to the following criteria.
○: Generation of cracks is not recognized.
Δ: Some cracks are observed.
X: Generation | occurrence | production of a crack is recognized.

[Evaluation of weather resistance (gloss retention)]
The specular reflectance (gloss value) (%) of the cured coating film for evaluation immediately after production and the cured coating film were converted into a dew panel light weather meter (manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m 2, 70 ° C. When wet: before exposure, the specular reflectance (gloss value) (%) of the coating film after 1,000 hours exposure at a humidity of 90% or higher, 50 ° C., light irradiation / wetting cycle = 8 hours / 4 hours) Retention rate (gloss retention rate:%) of the cured coating film with respect to the specular reflectance (gloss value) [(100 × specular reflectance of the coated film after exposure) / (mirror reflectance of the cured coating film before exposure)] It was evaluated with. It shows that a weather resistance is so favorable that the value of a retention rate is large.

  The evaluation results of Examples 1 to 9 are shown in Tables 1 and 2.

  Table 3 shows the evaluation results of the above Comparative Examples 1-6.

  The resin compositions of the present invention of Examples 1 to 9 are excellent in storage stability, and from these resin compositions, cured coating films excellent in various coating film properties such as heat resistance, solvent resistance, acid resistance, and weather resistance. It was confirmed that

  Comparative Examples 1 and 2 are examples in which the polysiloxane (a1) in the composite resin (A) is lower than 75% by mass which is the lower limit of the present invention, but the heat resistance of the obtained coating film is insufficient. Was confirmed.

  Although the comparative example 3 is an example which does not contain a polymer (a2), it was confirmed that storage stability is inadequate and coating film formation is inadequate.

  Comparative Example 4 is an example in which the structural unit (U1) in the polysiloxane (a1) is less than 10% by mass which is the lower limit of the present invention, but the storage stability is insufficient, and the resulting coating film is white. It was confirmed that the appearance of the coating film was insufficient and the adhesion and heat resistance were insufficient.

  Although the comparative example 5 is an example which does not have a structural unit (U2) in polysiloxane (a1), it was confirmed that the weather resistance of the coating film obtained is inadequate.

  Comparative Example 6 was an example in which a polysiloxane solution and a vinyl polymer solution were blended, but it was confirmed that the storage stability was insufficient and the coating film formation was insufficient.

（一般式（１）、（２）中のＲ^１は芳香族炭化水素置換基を表し、Ｒ^２は芳香族炭化水素
置換基又はアルキル基を表す。）

(R ¹ in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R ² represents an aromatic hydrocarbon substituent or an alkyl group.)

Claims (4)

The polysiloxane (a1) and the polymer (a2) having the structural unit (U1) represented by the general formula (1) or (2) and the structural unit (U2) represented by the general formula (3) are generally used. The composite resin (A) bonded by the bond represented by the formula (4) is a curable resin composition dissolved or dispersed in a medium, and the polysiloxane (a1) in the composite resin (A) ) Is 75 to 99% by mass, and the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

(R ¹ in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R ² represents an aromatic hydrocarbon substituent or an alkyl group.)

(R ³ in the general formula (3) represents a methyl group or an ethyl group.)

  The curable resin composition according to claim 1, wherein the structural unit (U1) is a structural unit derived from phenyltrimethoxysilane or diphenyldimethoxysilane.   A coating agent comprising the curable resin composition according to claim 1 or 2.   An article comprising the coating film of the coating agent according to claim 3.