JP4488123B1 - Coating agent for plastic substrate and laminate using the same - Google Patents

Abstract

The problem to be solved by the present invention is to provide a coating agent capable of forming a coating film that can achieve both excellent adhesion to various types of plastic substrates and excellent weather resistance. is there.
The present invention comprises a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), and an aqueous medium, The present invention relates to a coating agent for plastic substrates, wherein the mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 15 to 55% by mass.
[Selection figure] None

Description

  The present invention relates to a coating agent for plastic substrates that can be used for surface coating of various plastic substrates including transparent plastic substrates.

  The coating agent is required not only to impart design properties to various substrates, but also to form a coating film having excellent weather resistance and durability that can prevent deterioration of the substrate. Particularly in recent years, even when an organic solvent or acid rain adheres to the surface of the coating film, it has a level of weather resistance that does not cause dissolution or peeling of the coating film, reduction in gloss, occurrence of cracks, etc. The coating agent which can form the provided coating film is calculated | required from the industry.

  As a coating agent that can form a coating film having excellent weather resistance and the like, for example, a composite resin composed of a specific polysiloxane segment (A) and a polymer segment (B) having a hydrophilic group ( An aqueous resin obtained by mixing a mixture of C) and a specific polysiloxane (D) and condensing a part thereof as necessary is dispersed in an aqueous medium (for example, see Patent Document 1). ).

  Moreover, the coating agent which can form the said coating film which has the said weather resistance etc. is often calculated | required by the surface protection use of the plastic product which tends to cause deterioration by adhesion | attachment of acid rain etc.

  Examples of the plastic products include mobile phones, home appliances, OA equipment, automobile interior materials, and the like, and plastic materials having characteristics corresponding to applications and the like are used for such products.

  Various types of plastic materials have been developed. For example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), poly There are various types such as methyl methacrylate resin (PMMA resin).

  However, some plastic materials, such as polymethyl methacrylate resin, are generally known as substrates that are difficult to adhere to a coating film, and are superior to such difficult-to-adhere plastic substrates. There is a need to develop coating agents with excellent adhesion.

  Examples of the coating agent having good adhesion to the plastic substrate include an acrylic resin obtained by polymerizing a polymerizable monomer containing 70 to 95% by weight of methyl methacrylate, and 50% by weight or less of methyl. A coating composition for plastics containing an urethanized adduct composed of an acrylic resin obtained by polymerizing methacrylate, 3 mol of hexamethylene diisocyanate and 1 mol of trimethylolpropane is known (see, for example, Patent Document 2). .)

  On the other hand, the use of the plastic substrate is expected to further expand in the future, and it is also considered to apply it to a use that is exposed to the outdoor environment for a long time such as an automobile part.

  Under such circumstances, development of a coating composition capable of forming a coating film having a weather resistance level capable of preventing deterioration of a plastic substrate even when exposed to sunlight, wind and rain for a long time. However, the aqueous resin described in Document 1 cannot provide good adhesion to the hardly-adhesive plastic substrate, and the plastic coating composition described in Document 2 is long. When exposed to sunlight, wind and rain over a period of time, the coating film partially dissolved and peeled off, and as a result, the plastic substrate could be deteriorated.

  As described above, although there is a strong demand from the industry for a coating agent that can form a coating film that achieves both excellent adhesion to a plastic substrate and excellent weather resistance, the actual situation has yet to be found. It is.

JP-A-11-279408 JP 2003-253021 A

  The problem to be solved by the present invention is a coating for a plastic substrate that has excellent adhesion to various types of commonly known plastic substrates and that can form a coating film with excellent weather resistance. Is to provide an agent.

  The inventors of the present invention have made studies based on a coating agent of a type in which a resin is dissolved or dispersed in an aqueous medium and has a low environmental load. Specifically, an aqueous coating agent containing a vinyl polymer, which is generally known as being capable of improving the durability and weather resistance of a coating film, and a urethane resin that imparts good adhesion to a plastic substrate was examined.

  However, the water-based coating agent cannot form a coating film having a weather resistance of a practically required level, and it cannot be said that the adhesion to a plastic substrate is sufficient.

  Considering the use of polysiloxane, which is known as a structure consisting of silicon-oxygen bonds with high bonding strength, considering that imparting excellent weather resistance, etc. to the coating film may be achieved by increasing the crosslinking density of the coating film. did. Specifically, a coating agent in which polysiloxane was further mixed in addition to the urethane resin and the vinyl polymer was examined.

  However, even with the coating agent, it is impossible to form a coating film having a level of weather resistance or the like required for practical use, and the adhesion to a plastic substrate is not sufficient.

  As the inventors further studied, the present inventors studied an aqueous coating agent containing a resin in which the urethane resin, vinyl polymer, and polysiloxane were chemically bonded. Specifically, an aqueous coating agent in which a vinyl polymer and the hydrophilic group-containing polyurethane were chemically bonded via a polysiloxane structure was examined.

  However, even the aqueous coating agent is still not sufficient in terms of weather resistance.

  Therefore, the present inventors can form a coating film having practically sufficient weather resistance by using a coating agent containing a resin in which the mass ratio of the polysiloxane-derived structure in the resin is increased. We thought that it might be, and proceeded with examination.

  As a result, a composite resin in which a hydrophilic group-containing polyurethane and a vinyl polymer are bonded via polysiloxane, wherein the polysiloxane is included in a range of 15 to 55% by mass with respect to the entire composite resin. It has been found that when used, it is possible to form a coating film having both adhesion to a plastic substrate and weather resistance. Moreover, it discovered that the said coating film was excellent also in durability and base-material followability in addition to the adhesiveness and weather resistance with respect to the said plastic base material.

〔一般式（I）及び（II）中のＲ ^１ はケイ素原子に結合した炭素数が４〜１２の有機基、Ｒ ^２ 及びＲ ^３ は、それぞれ独立してケイ素原子に結合したメチル基又はケイ素原子に結合したエチル基を表す。〕
That is, the present invention is a hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) and a composite resin bound via a polysiloxane (a3) (A), and, and also contains an aqueous medium, wherein The bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) has the hydrolyzable silyl group and / or silanol group and the polysiloxane (a3) of the hydrophilic group-containing polyurethane (a1). It is formed by reaction with a hydrolyzable silyl group and / or silanol group, and the vinyl polymer (a2) has a bond between the vinyl polymer (a2) and the polysiloxane (a3). For the reaction between the hydrolyzable silyl group and / or silanol group and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3). The polysiloxane (a3) is a polysiloxane (a3-1) having at least one structure selected from the group consisting of the following general formulas (I) and (II), an alkyl The alkyltrialkoxysilane condensate (a3-2) having 1 to 3 carbon atoms bonded via a bond between a silicon atom and an oxygen atom, and derived from the polysiloxane (a3) Is contained in the range of 15 to 55% by mass with respect to the entire composite resin (A).

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ]

〔一般式（I）及び（II）中のＲ ^１ はケイ素原子に結合した炭素数が４〜１２の有機基、Ｒ ^２ 及びＲ ^３ は、それぞれ独立してケイ素原子に結合したメチル基又はケイ素原子に結合したエチル基を表す。〕
（１）有機溶剤の存在下で、加水分解性シリル基含有ビニル単量体及びシラノール基含有ビニル単量体からなる群より選ばれる１種以上を含むビニル単量体を重合することによってビニル重合体（ａ２）の有機溶剤溶液を得る工程、
（２）前記ビニル重合体（ａ２）の有機溶剤溶液の存在下で、前記ビニル重合体（ａ２）とシラン化合物とを反応させることによって、ビニル重合体（ａ２）にポリシロキサン（ａ３）が結合した樹脂（Ｃ）の有機溶剤溶液を得る工程、
（３）前記樹脂（Ｃ）と、加水分解性シリル基及び／またはシラノール基を有する親水性基含有ポリウレタン（ａ１）とを混合し、前記樹脂（Ｃ）中の前記ポリシロキサン（ａ３）が有する加水分解性シリル基及び／またはシラノール基と、前記親水性基含有ポリウレタン（ａ１）が有する加水分解性シリル基及び／またはシラノール基とを反応させることによって、前記ビニル重合体（ａ２）と親水性基含有ポリウレタン（ａ１）とが前記ポリシロキサン（ａ３）を介して結合した複合樹脂（Ａ）の有機溶剤溶液を得る工程、
（４）有機溶剤中の前記複合樹脂（Ａ）の有する親水性基を中和し、該中和物を含む有機溶剤溶液と水系媒体とを混合することで前記中和物を水系媒体中に溶解または分散する工程。
Moreover, this invention is a manufacturing method of the coating agent for plastic substrates which consists of the process of the following (1)-(4), Comprising : The said coating agent for plastic substrates is hydrophilic group containing polyurethane (a1), and A composite resin (A) in which a vinyl polymer (a2) is bonded via a polysiloxane (a3) and an aqueous medium, the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) Is formed by a reaction between the hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3). And the bond between the vinyl polymer (a2) and the polysiloxane (a3) is added to the water added to the vinyl polymer (a2). It is formed by a reaction between a decomposable silyl group and / or silanol group and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3), and the polysiloxane (a3) has the following general formula: Condensate (a3-2) of polysiloxane (a3-1) having at least one structure selected from the group consisting of (I) and (II) and alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group ) Are bonded via a bond between a silicon atom and an oxygen atom, and the structure derived from the polysiloxane (a3) is in the range of 15 to 55% by mass with respect to the entire composite resin (A). It is related with the manufacturing method of the coating agent for plastic substrates which is contained in .

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ]
(1) By polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer in the presence of an organic solvent, A step of obtaining an organic solvent solution of the combined (a2),
(2) The polysiloxane (a3) is bonded to the vinyl polymer (a2) by reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2). A step of obtaining an organic solvent solution of the obtained resin (C),
(3) The resin (C) and the hydrophilic group-containing polyurethane (a1) having a hydrolyzable silyl group and / or silanol group are mixed, and the polysiloxane (a3) in the resin (C) has. By reacting the hydrolyzable silyl group and / or silanol group with the hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) , the vinyl polymer (a2) and the hydrophilic group are made hydrophilic. A step of obtaining an organic solvent solution of the composite resin (A) in which the group-containing polyurethane (a1) is bonded via the polysiloxane (a3);
(4) The hydrophilic group of the composite resin (A) in the organic solvent is neutralized, and the neutralized product is mixed into the aqueous medium by mixing the organic solvent solution containing the neutralized product with the aqueous medium. The process of dissolving or dispersing.

  The coating agent for a plastic substrate of the present invention has a coating film having excellent adhesion to a plastic substrate, excellent weather resistance, and also having durability and substrate followability. Because it can be formed, for example, an automobile interior material in which a substrate such as a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacryl substrate, a polystyrene substrate, a polyurethane substrate, and an epoxy resin substrate is used. Coatings for surface coating and primer layer formation for optical films, light diffusion films, mobile phones, home appliances, office automation equipment, etc. used in glass, organic glass, electrical and construction materials, building exterior materials, liquid crystal displays, etc. Can be used for

  Moreover, since the coating agent for plastic base materials of this invention can form the coating film which is excellent in base material followability, it can be used also for the surface coating etc. of the various functional films which comprise a polarizing plate, for example.

  The present invention relates to a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), an aqueous medium, and other additives as required. A plastic base coating agent characterized in that the mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 15 to 55% by mass. is there.

  The composite resin (A) is dispersed in an aqueous medium, but a part of the composite resin (A) may be dissolved in the aqueous medium. The composite resin (A) dispersed in the aqueous medium has a mean particle size of 10 to 500 nm, and has excellent substrate followability such as crack resistance, and excellent durability and weather resistance. It is preferable when forming a film. Here, the average particle diameter refers to a value measured by a method for obtaining a particle size distribution by a measurement principle for detecting dynamic scattered light of particles.

  Further, the followability of the coating film to the plastic substrate means that when the plastic substrate is slightly expanded or contracted due to the influence of heat or the like, the coating film on the surface of the substrate is expanded or contracted. It is a property that can follow. If the coating film is relatively hard like conventional products, it cannot follow the expansion and contraction of the plastic substrate, resulting in cracks in the coating film, and deterioration of the plastic substrate in the cracked part. May be caused. On the other hand, since the coating agent of the present invention can form a relatively flexible coating film, it can form a coating film in which cracks and the like are unlikely to occur.

  The composite resin (A) is excellent in adhesion to a plastic substrate and has a durability and weather resistance of 15 to 55% by mass with respect to the entire composite resin (A). It is important to have a structure derived from the polysiloxane (a3). For example, in the composite resin in which the mass ratio of the polysiloxane (a3) is 10% by mass, a coating film still having a sufficient level in terms of weather resistance cannot be formed, and also in terms of substrate followability and durability. A coating film having a sufficient level cannot be formed, and peeling or dissolution from the substrate may occur over time.

  On the other hand, a composite resin containing a composite resin in which the mass ratio of the polysiloxane (a3) exceeds 55 mass%, specifically, the mass ratio of the structure derived from the polysiloxane (a3) is 65 mass%. The coating agent may cause a significant increase in viscosity due to the hydrolytic condensation reaction of polysiloxane and may cause gelation. Further, as the mass ratio of the structure derived from the hydrophilic group-containing polyurethane (a1) or the vinyl polymer (a2) is lowered, the film forming property is lowered, and as a result, cracks are generated on the coating film surface, There may be a significant decrease in the substrate follow-up properties and substrate adhesion of the coating.

  The mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is preferably in the range of 20% by mass to 50% by mass, and in the range of 20% by mass to 35% by mass. It is preferable for forming a coating film having excellent durability, weather resistance, and substrate followability, and also having adhesion to a plastic substrate.

  The structure derived from the polysiloxane (a3) means that the main chain constituting the connecting portion between the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) constituting the composite resin (A) is an oxygen atom. And a silicon atom. Further, the mass ratio of the structure derived from the polysiloxane (a3) is methanol that can be generated by a hydrolysis condensation reaction of the polysiloxane (a3) or the like based on the charging ratio of the raw material used for the production of the composite resin (A). And a value calculated in consideration of the formation of by-products such as ethanol.

  The composite resin (A) must have a hydrophilic group in order to be stably dissolved or dispersed in an aqueous medium.

  The hydrophilic group is essential to be present mainly in the polyurethane (a1) constituting the outer layer of the composite resin (A), but if necessary, it is present in the vinyl polymer (a2). Also good.

  As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used, and it is more preferable to use an anionic group.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used. Among them, a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in producing a composite resin having good water dispersibility.

  Examples of basic compounds that can be used for neutralization of the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base compound etc. are mentioned.

  When a carboxylate group or a sulfonate group is used as the anionic group, it is preferable that they are present in a range of 50 to 1000 mmol / kg with respect to the entire composite resin (A). It is preferable for maintaining the dispersion stability.

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used when neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more.

  Examples of the quaternizing agent that can be used for quaternizing a part or all of the tertiary amino group include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, and ethyl chloride. Alkyl halides such as benzyl chloride, alkyls such as methyl methanesulfonate and methyl paratoluenesulfonate, and epoxies such as ethylene oxide, propylene oxide, and epichlorohydrin may be used alone or in combination of two or more.

  Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

  Moreover, as said composite resin (A), mass ratio [(a2) / (a1)] of the said hydrophilic group containing polyurethane (a1) and the said vinyl polymer (a2) is 20/1-1/20. It is preferable to use what is the range of this, 15/1-1/20 are more preferable, 10/1-1/20 are more preferable, 5/1-1/20 are especially preferable. Especially, it is especially preferable that it is the range of 1/1-1/12 when forming the coating film which can be compatible with the adhesiveness with respect to a plastic base material, and a weather resistance, and was excellent in base material followability.

  The bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) is, for example, the hydrolyzable silyl group and / or silanol group and the polysiloxane (the hydrophilic group-containing polyurethane (a1)). It is preferably formed by a reaction with a hydrolyzable silyl group and / or silanol group possessed by a3). Further, the bond between the vinyl polymer (a2) and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group possessed by the vinyl polymer (a2) and a hydrolyzate possessed by the polysiloxane (a3). It is preferably formed by a reaction with a decomposable silyl group and / or silanol group.

  Next, the hydrophilic group-containing polyurethane (a1) constituting the composite resin (A) will be described.

  The hydrophilic group-containing polyurethane (a1) is an essential component for imparting excellent adhesion to a plastic substrate and substrate compliance to the coating agent for a plastic substrate of the present invention.

  As the hydrophilic group-containing polyurethane (a1), various types can be used. For example, those having a number average molecular weight of 3000 to 100,000 are preferably used, and have a number average molecular weight of 5000 to 10,000. It is preferable to use a material for forming a coating film excellent in weather resistance, substrate followability and durability.

  Moreover, as the hydrophilic group-containing polyurethane (a1), it is particularly preferable to use one having a structural unit derived from a polycarbonate polyol in order to further improve the excellent adhesion to a plastic substrate.

  The hydrophilic group-containing polyurethane (a1) must have a hydrophilic group in order to impart water dispersion stability to the composite resin (A). The hydrophilic group is preferably present in the range of 50 to 1000 mmol / kg with respect to the entire hydrophilic group-containing polyurethane (a1) in order to impart better water dispersibility to the composite resin.

  As said hydrophilic group containing polyurethane (a1), the polyurethane obtained by making a polyol and polyisocyanate react can be used, for example. The hydrophilic group contained in the hydrophilic group-containing polyurethane (a1) is introduced into the hydrophilic group-containing polyurethane (a1), for example, by using the hydrophilic group-containing polyol as one component constituting the polyol. be able to.

  As a polyol that can be used for the production of the hydrophilic group-containing polyurethane (a1), for example, the hydrophilic group-containing polyol and other polyols can be used in combination.

  Examples of the hydrophilic group-containing polyol include carboxyl groups such as 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolvaleric acid. Containing polyols and sulfonic acid group-containing polyols such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used. The hydrophilic group-containing polyol is obtained by reacting the above-described low molecular weight hydrophilic group-containing polyol such as carboxyl group-containing polyol or sulfonic acid group-containing polyol with various polycarboxylic acids such as adipic acid. Hydrophilic group-containing polyester polyols and the like that can be used can also be used.

  Other polyols that can be used in combination with the hydrophilic group-containing polyol are appropriately used according to the characteristics required for the coating material for plastic substrates of the present invention, the application to which the coating material for plastic substrates is applied, and the like. For example, polycarbonate polyol, polyether polyol, polyester polyol and the like can be used. Of these, the use of polycarbonate polyol is preferable in order to further improve the adhesion to the plastic substrate. The other polyol may or may not have a hydrophilic group.

  The polycarbonate polyol that can be used for the production of the hydrophilic group-containing polyurethane (a1) is preferable for significantly improving the adhesion of the coating agent of the present invention to the plastic substrate.

  As said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, and what is obtained by making phosgene, bisphenol A, etc. react can be used. The polycarbonate polyol may or may not have a hydrophilic group.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  As the polycarbonate polyol, use of a product obtained by reacting the dimethyl carbonate and the 1,6-hexanediol achieves both excellent adhesion to a plastic substrate and excellent substrate followability. It is more preferable because it is possible and inexpensive.

  Moreover, as said polycarbonate polyol, it is preferable to use what has the number average molecular weight of the range of 500-6000.

  The polycarbonate polyol is used in the range of 30 to 95% by mass with respect to the total amount of polyol and polyisocyanate used in the production of the polyurethane (a1), and thus has an adhesion property, weather resistance and durability to a plastic substrate. It is preferable to achieve both.

  The coating agent of the present invention obtained using the polycarbonate polyol includes, among others, a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacryl substrate, a polystyrene substrate, a polyurethane substrate, and an epoxy resin group. Materials, polyvinyl chloride base materials, polyamide base materials, and other various plastic base materials generally known as hard-to-adhere base materials, and particularly excellent adhesion,

  In addition, as the polyether polyol that can be used for the other polyols, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator may be used. it can.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Examples of the polyester polyol that can be used as the other polyol include cyclic ester compounds such as aliphatic polyester polyols, aromatic polyester polyols, and ε-caprolactone obtained by esterifying low molecular weight polyols and polycarboxylic acids. Polyester obtained by ring-opening polymerization reaction, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.

  Examples of the polycarboxylic acid that can be used include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

  As the polyol used for the production of the hydrophilic group-containing polyurethane (a1), the polycarbonate polyol and the hydrophilic group-containing polyol are used in combination depending on the type of the plastic substrate and its surface state, use, etc. If necessary, a polyester polyol or a polyether polyol as described above may be further used in combination.

  Examples of the polyisocyanate used in producing the hydrophilic group-containing polyurethane (a1) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, Aliphatic or aliphatic cyclic structure-containing diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate can be used alone or in combination of two or more. . Among them, it is preferable to use an aliphatic cyclic structure-containing diisocyanate because a coating film having excellent long-term weather resistance can be formed.

  The hydrophilic group-containing polyurethane resin (a1) may have other functional groups as needed in addition to the hydrophilic groups as described above. Examples of such functional groups include polysiloxane (described later) Examples thereof include hydrolyzable silyl groups, silanol groups, amino groups, imino groups, hydroxyl groups and the like that can react with a3). Among them, polysiloxane (a3) has hydrolyzable silyl groups and silanol groups. Forming a bond with a hydrolyzable silyl group or silanol group is preferable because a coating film having excellent long-term weather resistance can be formed.

  The hydrolyzable silyl group that the hydrophilic group-containing polyurethane (a1) may have is a functional group in which the hydrolyzable group is directly bonded to a silicon atom, and is represented by, for example, the following general formula (III). Functional groups that can be used.

Wherein R ¹ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, R ² 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 x is an integer of 0 to 2.)

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the group include an allyloxy group, a 1-propenyloxy group, and an isopropenyloxy group.

R ² is preferably independently an alkoxy group, since it is easy to remove a leaving component such as the general formula R ² OH that can be generated by hydrolysis.

  Further, the silanol group that the hydrophilic group-containing polyurethane (a1) may have is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and the hydrolyzable silyl group described above is mainly hydrolyzed. The resulting functional group.

  As a method for introducing the functional group represented by the general formula (III) such as the hydrolyzable silyl group or the silanol group into the hydrophilic group-containing polyurethane (a1), for example, the polyol and the polyisocyanate are [isocyanate group / The urethane prepolymer having an isocyanate group at the molecular end is obtained by reacting in the range where the equivalent ratio of the hydroxyl group is 1.1 to 5, and then the isocyanate group possessed by the urethane prepolymer and, for example, 3-aminopropyltrimethyl Examples thereof include a method of reacting an amino group-containing silane compound such as ethoxysilane or 3-aminopropyltrimethoxysilane.

  The hydrolyzable silyl group and silanol group are present in an amount of 10 to 400 mmol / kg with respect to the entire hydrophilic group-containing polyurethane (a1) in order to ensure good water dispersion stability of the composite resin (A). Is preferable.

Next, the vinyl polymer (a2) constituting the composite resin (A) will be described.
The vinyl polymer (a2) can be bonded to the hydrophilic group-containing polyurethane (a1) via a polysiloxane (a3) described later.

  As the vinyl polymer (a2), those having a number average molecular weight of 3000 to 100,000 are preferably used, and those having a number average molecular weight of 5,000 to 25000 are excellent in substrate followability, And it is more preferable when forming the coating film excellent in durability, such as crack resistance, and a weather resistance.

  As said vinyl polymer (a2), what was manufactured by superposing | polymerizing various vinyl monomers in presence of a polymerization initiator can be used, for example.

  From the viewpoint of introducing a functional group capable of reacting with the hydrolyzable silyl group and the like of the polysiloxane (a3) into the vinyl polymer (a2), the vinyl monomer is hydrolyzable silyl group or silanol. It is preferable to use a group-containing vinyl monomer or a hydroxyl group-containing vinyl monomer.

  Examples of the hydrolyzable silyl group and / or silanol group-containing vinyl monomer include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyl. Oxypropylmethyldimethoxysilane and the like can be used, and among them, 3- (meth) acryloyloxypropyltrimethoxysilane is preferably used.

  In addition, as the hydroxyl group-containing vinyl monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, or the like is used. Can do.

  As the vinyl monomer, in addition to the hydrolyzable silyl group-containing vinyl monomer and the hydroxyl group-containing vinyl monomer, other vinyl monomers may be used in combination as necessary.

  Examples of the other vinyl monomers include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate; N, N-dimethylaminoethyl (meth) Tertiary amino group-containing vinyl monomers such as acrylates; Secondary amino group-containing vinyl monomers such as N-methylaminoethyl (meth) acrylate; Bases such as primary amino group-containing vinyl monomers such as aminomethyl acrylate Nitrogen-containing group-containing vinyl monomers; fluorine-containing vinyl monomers such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether; ) Nitriles of unsaturated carboxylic acids such as acrylonitrile; vinyl compounds having an aromatic ring such as styrene Α-olefins such as isoprene; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; amide group-containing vinyl monomers such as (meth) acrylamide; methylolamide groups such as N-methylol (meth) acrylamide; An alkoxy compound-containing vinyl monomer; 2-aziridinylethyl (meth) acrylate-containing vinyl monomer; an isocyanate group such as (meth) acryloyl isocyanate and / or a blocked isocyanate group-containing vinyl Monomer; Oxazoline group-containing vinyl monomer such as 2-isopropenyl-2-oxazoline; Cyclohexyl (meth) acrylate; Cyclopentenyl group-containing vinyl monomer such as dicyclopentenyl (meth) acrylate; Carbonyl such as acrolein Group-containing vinyl monomer; Acetoacetyl group-containing vinyl monomers such as cetoacetoxyethyl (meth) acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, or half-esters thereof, or salts thereof, etc. More than seeds can be used.

  Examples of the polymerization initiator that can be used in producing the vinyl polymer (a2) include radical polymerization initiators such as persulfates, organic peroxides, and hydrogen peroxide, and 4,4′-azobis ( An azo initiator such as 4-cyanovaleric 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.

  Examples of the persulfates that are representative of the polymerization initiator include potassium persulfate, sodium persulfate, and ammonium persulfate. Specific examples of organic peroxides include, for example, peroxidation. Diacyl peroxides such as benzoyl, lauroyl peroxide, decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, etc. Peroxyesters, cumene hydroperoxide, paramentane hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, and the like 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.

Next, the polysiloxane (a3) constituting the composite resin (A) will be described.
The polysiloxane (a3) constitutes a connecting portion between the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2).

  The polysiloxane (a3) has a chain structure composed of silicon atoms and oxygen atoms, and has a hydrolyzable silyl group, a silanol group, or the like as necessary.

  The hydrolyzable silyl group is an atomic group in which the hydrolyzable group is directly bonded to the silicon atom. For example, the hydrolyzable silyl group is represented by the general formula (III) exemplified in the description of the hydrophilic group-containing polyurethane (a1). The thing which consists of such a structure is mentioned.

  The hydrolyzable silyl 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 indicates 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.

  Moreover, as said polysiloxane (a3), what has alkyl groups, such as a methyl group, a phenyl group, etc. other than what was mentioned above as needed can be used, for example, polysiloxane (a3) 1 or more selected from the group consisting of an aromatic cyclic structure such as a phenyl group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. It is more preferable to use those in which are directly bonded in order to maintain good water dispersion stability of the composite resin.

  As said polysiloxane (a3), what is obtained, for example by hydrolyzing and condensing the silane compound mentioned later completely or partially can be used.

  Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, and phenyltrimethoxysilane. Organotrialkoxysilanes such as methoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloyloxypropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane , Diorganodialkoxysilanes such as diphenyldimethoxysilane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane Various chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or diphenyldichlorosilane, and their partial hydrolysis A decomposition condensate or the like can be used, and among them, organotrialkoxysilane and diorganodialkoxysilane are preferably used. These silane compounds may be used alone or in combination of two or more.

  Moreover, as said polysiloxane (a3), carbon number of the polysiloxane (a3-x) which has 1 or more types of structures chosen from the group which consists of the following general formula (I) and (II), and an alkyl group is 1 It is preferable that a condensate (a3-y) of ~ 3 alkyltrialkoxysilane is bonded via a bond between a silicon atom and an oxygen atom in order to form a coating film having excellent weather resistance. .

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ]

  The polysiloxane (a3-x) having the structure represented by the general formulas (I) and (II) is an organoalkoxysilane, preferably a monoorgano having an organic group having 4 to 12 carbon atoms bonded to a silicon atom. Use a trialkoxysilane, a diorganodialkoxysilane having two methyl groups bonded to a silicon atom, and a diorganodialkoxysilane having two ethyl groups bonded to a silicon atom, hydrolyzed and condensed. It may have any structure of linear, branched, and annular.

  Examples of the organic group having 4 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 4 to 12 carbon atoms, such as an n-butyl group and an iso-butyl group. Alkyl groups such as n-hexyl group, n-octyl group, n-dodecyl group and cyclohexylmethyl group; cycloalkyl groups such as cyclohexyl group and 4-methylcyclohexyl group; aryl groups such as phenyl group and 4-methylphenyl group An aralkyl group such as a benzyl group is preferable, and a phenyl group or an alkyl group having 4 carbon atoms is more preferable.

  Moreover, as a condensate (a3-y) of the alkyltrialkoxysilane having 1 to 3 carbon atoms of the alkyl group, for example, one having a hydroxyl group bonded to a silicon atom and an alkoxy group bonded to a silicon atom is used. can do.

  Specifically, as the alkyltrialkoxysilane condensate (a3-y), it is possible to use a film having a structure represented by the following general formula (IV) to form a coating film having excellent weather resistance. In addition, it is preferable.

[R ⁴ in the general formula (IV) is an alkyl group having 1 to 3 carbon atoms. ]

  Moreover, it is preferable to form the said polysiloxane (a3) by passing through a two-step reaction process in the process of manufacturing composite resin (A). Specifically, a relatively low molecular weight silane compound such as phenyltrimethoxysilane exemplified as the polysiloxane (a3-x) is reacted with the hydrolyzable group or the like of the vinyl polymer (a2). Then, the polysiloxane structure is formed, and then the reaction product is reacted with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane as exemplified by the alkyltrialkoxysilane condensate (a3-y). By doing so, a structure made of polysiloxane (a3) can be formed. Thereby, the coating agent for plastic base materials which can form the coating film which was further excellent in the adhesiveness and followable | trackability with respect to a plastic base material, and was excellent in durability and stain resistance can be obtained.

  Next, the manufacturing method of the coating agent for plastic base materials used by this invention is demonstrated.

  The method for producing a coating material for a plastic substrate of the present invention mainly comprises a step of producing a composite resin (A) and a step of dispersing the composite resin (A) in an aqueous medium.

  First, the process for producing the composite resin (A) will be described.

  The composite resin (A) can be produced, for example, by the following steps (1) to (3).

  The step (1) is a step of obtaining an organic solvent solution of the vinyl polymer (a2) by polymerizing the vinyl monomer in the presence of the polymerization initiator in an organic solvent. Specifically, radical polymerization of a vinyl monomer containing at least one selected from the group consisting of the hydrolyzable silyl group-containing vinyl monomer and the silanol group-containing vinyl monomer in the presence of a polymerization initiator is performed. And a step of obtaining an organic solvent solution of a vinyl polymer having a hydrolyzable silyl group and / or a silanol group.

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

  In the step (2), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a2) under the organic solvent solution of the vinyl polymer (a2) and a hydrolyzate possessed by the silane compound. The organic of the resin (C) in which the vinyl polymer (a2) and the polysiloxane (a3) are bonded by a reaction with a decomposable silyl group or silanol group and a hydrolysis condensation reaction between the silane compounds. This is a step of obtaining a solvent solution.

  In the reaction, for example, following the step (1), the silane compound capable of forming the polysiloxane (a3) is sequentially or collectively supplied into the organic solvent solution of the vinyl polymer, and then stirred. It is preferable to carry out in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  The step (2) preferably further undergoes a two-step reaction step. Specifically, a step of reacting the hydrolyzable silyl group or silanol group of the vinyl polymer with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then reacting the reaction product with methyl It is preferable to undergo a step of reacting a condensate obtained by condensing methyltrialkoxysilane and ethyltrialkoxysilane in advance such as trimethoxysilane and ethyltrimethoxysilane. By forming the polysiloxane (a3) structure in the two steps as described above, it is possible to form a coating film that is even more excellent in adhesion to plastic substrates and excellent in substrate follow-up and durability. A coating agent for a plastic substrate can be obtained.

  In the step (3), the resin (C) and the hydrophilic group-containing polyurethane (a1) are mixed and hydrolytically condensed, whereby the vinyl polymer (a2) and the hydrophilic group-containing polyurethane ( a1) is a step of obtaining an organic solvent solution of the composite resin (A) bonded with the polysiloxane (a3).

  For example, following the step (2), the reaction may be carried out by reacting a polyol containing the hydrophilic group-containing polyol with the polyisocyanate in an organic solvent solution of the resin (C). It is preferable to supply the polyurethane-containing (a1) sequentially or collectively, and then perform the stirring in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  Moreover, the said composite resin (A) can also be manufactured, for example by the following processes (X)-(Y).

  The step (X) is a step of producing a vinyl-polyurethane resin by reacting the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) in the presence of an organic solvent. Specifically, the hydrolyzable silyl group and / or silanol group introduced into the hydrophilic group-containing polyurethane (a1), and the hydrolyzable silyl group and / or silanol group introduced into the vinyl polymer (a2) Is a step of forming a bond by hydrolytic condensation reaction.

  The hydrolysis-condensation reaction between the hydrolyzable silyl group and / or silanol group is preferably performed, for example, in an environment of about 40 to 100 ° C. for about 1 to 24 hours.

  In the step (Y), the organic solvent solution of the composite resin (A) is prepared by mixing and reacting the organic solvent solution of the vinyl-polyurethane resin obtained in the step (X) with the polysiloxane (a3). This is a process for producing a solution. Specifically, the hydrolyzable silyl group and / or silanol group possessed by the vinyl-polyurethane resin obtained in the step (X), and the hydrolyzable silyl group and / or silanol group possessed by the polysiloxane (a3). And a hydrolytic condensation reaction to form a bond.

  The hydrolytic condensation reaction between the hydrolyzable silyl group and / or silanol group is preferably performed, for example, in an environment of 40 to 100 ° C. for about 1 to 24 hours.

  Moreover, it is preferable to form the said polysiloxane (a3) by passing through a two-step reaction process in the process of manufacturing composite resin (A). Specifically, phenyltrimethoxysilane or the like exemplified as the polysiloxane (a3-x) is present in the hydrolyzable silyl group and / or silanol group of the vinyl-polyurethane resin obtained in the step (X). A polysiloxane structure is formed by reacting a silane compound having a relatively low molecular weight, and then methyltrimethoxysilane or ethyl as exemplified as a condensate (a3-y) of the reaction product and the alkyltrialkoxysilane. By reacting with a condensate such as trimethoxysilane, a structure composed of polysiloxane (a3) can be formed. Thereby, the coating agent for plastic base materials which can form the coating film which was further excellent in the adhesiveness and followable | trackability with respect to a plastic base material, and was excellent in durability and stain resistance can be obtained.

  The organic solvent solution of the composite resin (A) obtained by the steps (1) to (3) and the steps (X) to (Y) is preferably made aqueous by the following step (4).

  In the step (4), for example, following the step (3) and the step (Y), the hydrophilic group of the composite resin (A) is neutralized, and the neutralized product is dissolved or dispersed in an aqueous medium. It is a process to do.

  Neutralization of the hydrophilic group is not necessarily performed, but is preferably performed from the viewpoint of improving the water dispersion stability of the composite resin (A). In particular, when the hydrophilic group is an anionic group such as a carboxyl group or a sulfonic acid group, all or a part thereof is neutralized with a basic compound to form a carboxylate group or a sulfonate group. Is preferable for further improving the water dispersion stability.

  The neutralization can be performed, for example, by sequentially or collectively supplying a basic compound or the like into the organic solvent solution of the composite resin (A) and stirring.

  After the neutralization, an aqueous medium is supplied into the organic solvent solution of the neutralized product of the composite resin (A), and then, if necessary, the organic solvent is removed. Can be manufactured. The removal of the organic solvent can be performed, for example, by distillation.

  Moreover, as an aqueous medium used by this invention, the organic solvent mixed with water and water, and these mixtures are mentioned. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The coating agent for a plastic substrate of the present invention suppresses a sudden increase in viscosity during production, and also improves the productivity of the coating agent for a plastic substrate, ease of coating, drying properties, etc. From the above, it is preferable to have a nonvolatile content of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.

  Moreover, it is preferable to use a hardening | curing agent for the coating agent for plastic base materials of this invention from a viewpoint which provides much more excellent weather resistance and base-material adhesiveness.

  As said hardening | curing agent, when forming a coating film, the compound which has a functional group which reacts with the hydrophilic group which the said composite resin (A) has, a silanol group, etc. can be used.

  Specific examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate. In particular, when the composite resin having a carboxyl group or a carboxylate group is used, a combination using an epoxy group, a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound It is preferable that

  Examples of the compound having a silanol group and / or a hydrolyzable silyl group include those similar to the silane compounds exemplified as usable in the production of the composite resin, and other 3-glycidoxypropyltrimethoxy. Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These hydrolysis-condensation products are exemplified.

  Examples of the polyepoxy compound include polyglycidyl ethers having a structure derived from an aliphatic or alicyclic polyol such as ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A and the like. Polyglycidyl ethers of aromatic diols such as bisphenol A, bisphenol S and bisphenol F; polyglycidyl ethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; tris (2-hydroxyethyl) Polyglycidyl ethers of isocyanurates; polyglycidies of aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, phthalic acid, terephthalic acid Bisepoxides of hydrocarbon dienes such as cyclooctadiene and vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, etc. And alicyclic polyepoxy compounds.

  Examples of the polyoxazoline compound include 2,2′-p-phenylene-bis (1,3-oxazoline), 2,2′-tetramethylene-bis (1,3-oxazoline), and 2,2′-octa. Methylene-bis (2-oxazoline), 2-isopropenyl-1,3-oxazoline, or a polymer thereof can be used.

  Examples of the polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate; meta-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate Aralkyl diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane, isophorone Diisocyanate and the like can be used.

  As the polyisocyanate, various prepolymers having an isocyanate group, prepolymers having an isocyanurate ring, polyisocyanate having a biuret structure, and isocyanate group-containing vinyl monomers can also be used.

  The isocyanate group of the polyisocyanate as a curing agent may be blocked with a conventionally known blocking agent such as methanol as necessary.

  The curing agent is preferably used within a range of 0.1 to 50 parts by weight of solid content, for example, within a range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the composite resin (A). More preferably, it is particularly preferably used within the range of 1 to 20 parts by weight.

  Further, when the composite resin (A) has a carboxyl group as a hydrophilic group, the curing agent is an epoxy group or cyclocarbonate that the curing agent has for 1 equivalent of the carboxyl group in the composite resin (A). The equivalent of a reactive functional group such as a group, a hydroxyl group, an oxazoline group, a carbodiimide group, or a hydrazino group is preferably within a range of 0.2 to 5.0 equivalents, and within a range of 0.5 to 3.0 equivalents It is more preferable that it is in the range of 0.7 to 2.0 equivalents.

  Moreover, the coating agent for plastic substrates of the present invention can contain a curing catalyst as required.

  Examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, and zinc octylate. Calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, p-toluenesulfone Acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like can be used.

  The coating agent for a plastic substrate 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.

  Various inorganic particles such as clay mineral, metal, metal oxide, glass and the like can be used in the coating agent for a plastic substrate of the present invention as necessary. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

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

  The photocatalytic compound is a compound that oxidizes and decomposes organic substances by light irradiation, and has recently been attracting attention in fields where a self-cleaning function is required, such as for building exteriors. Photocatalytic compounds can also decompose harmful gases such as NOx in the atmosphere and environmental hormones in the water, and can also exhibit air purification, water purification, deodorization and antibacterial functions. It is also attracting attention as an environmentally useful material.

  Examples of the photocatalytic compound include titanium oxide, zinc oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, germanium oxide, copper oxide, vanadium oxide, manganese oxide, nickel oxide, and ruthenium oxide. can do. Specifically, for example, “ST-01” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 7 nm], “ST-21” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 20 nm], “ AMT-100 "[Titanium Co., Ltd., titanium oxide, average particle diameter 6 nm]," TKD-701 "[Taika Co., Ltd. titanium oxide dispersion, average particle diameter 6 nm]," TKD-702 "[Taika Corporation ) Titanium oxide dispersion, average particle size 6 nm], “STS-21” (Ishihara Sangyo Co., Ltd. titanium oxide water dispersion, average particle size 20 nm), “TKS-203” (Taika Co., Ltd.) Titanium aqueous dispersion, average particle diameter of 6 nm] and the like can be used. Of these, it is preferable to use titanium oxide or zinc oxide that is chemically stable, harmless, and has high photocatalytic activity.

  The photocatalytic compound is preferably in the form of particles, and the average particle diameter is usually 3 to 100 nm, preferably 3 to 50 nm, and particularly preferably 4 to 30 nm.

  As the photocatalytic compound, the fine powder may be used as it is, but from the viewpoint of imparting good dispersibility, a sol form in which the photocatalytic compound is dispersed in advance in an organic solvent or an aqueous medium. Are preferably used.

  The photocatalytic compound is preferably in the range of 0.01 to 20 parts by mass and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the composite resin (A). preferable. By using the photocatalytic compound within the above range, the effect of decomposition and degradation of the resulting coating film due to oxide fine particles is small, and the self-cleaning function of the coating film due to the hydrophilization of the coating surface layer part is exhibited. Can do.

  As the stabilizer, it is particularly preferable to use a stabilizer having a semicarbazide group or a stabilizer having a structure derived from a hindered amine.

  Examples of the stabilizer having the semicarbazide group include burette-tri (hexamethylene-N, N-dimethylsemicarbazide), 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1,1- Tetramethyl-4,4 (methylene-di-P-phenylene) semicarbazide or the like can be used.

  Examples of the stabilizer having a structure derived from the hindered amine include N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6). -Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2 , 2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine / N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, etc. Can do.

  Moreover, it is preferable to use an antioxidant having a phenol-derived structure as the antioxidant. Specifically, 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4,4′-butylidenebis (6-t- Butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] and the like.

  The coating agent of the present invention has excellent adhesion to various plastic substrates. Therefore, it can be suitably used as a coating agent for surface coating of plastic products, a coating agent for forming a primer coat layer, and the like.

  As the plastic substrate, generally used in plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, office automation equipment, light receiving surfaces and back surfaces of solar cells, polycarbonate substrates, polyester substrates, Use a plastic substrate selected from the group consisting of acrylonitrile-butadiene-styrene substrate, polyacryl substrate, polystyrene substrate, polyurethane substrate, epoxy resin substrate, polyvinyl chloride substrate and polyamide substrate. Can do.

  Moreover, since the coating agent for plastic substrates of this invention can form a comparatively transparent coating film, it can be used for the surface coating of a transparent plastic substrate, for example.

  Here, as the transparent plastic substrate, a substrate made of polymethyl methacrylate resin (PMMA resin), polycarbonate resin, or the like can be used. These transparent plastic substrates are commonly referred to as organic glass, and have characteristics such as being lighter and harder to break than general inorganic glass. In recent years, they have been used as substitutes for inorganic glass in window glass for houses and automobiles. The application of is being considered. According to the coating agent of the present invention, it is possible to impart excellent weather resistance, durability, contamination resistance, and the like to the organic glass without impairing the transparency of the organic glass used for window glass in houses and the like. it can.

  The various base materials described above may be coated in advance, but since the coating agent of the present invention has excellent adhesion to a plastic substrate or the like, surface treatment such as coating is performed in advance. Even if it is not a base material, it can be used without a problem.

  The base materials may be plate-shaped, spherical, film-shaped, and sheet-shaped, respectively. In addition, since the coating agent of the present invention is particularly excellent in substrate followability, a film-like or sheet-like substrate that tends to cause deformation or expansion / contraction due to the influence of external force or temperature, or a substrate having fine irregularities on the surface Can also be used suitably.

  The coating agent for a plastic substrate of the present invention is a coating material excellent in durability, weather resistance, adhesion, substrate followability, etc., for example, by directly applying it to the surface of the substrate, followed by drying and curing. A film can be formed.

  Examples of the method for applying the coating agent for a plastic substrate on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  Examples of the drying and curing method include a method of curing for about 1 to 10 days at room temperature. From the viewpoint of rapidly curing, heating at a temperature of 30 to 250 ° C. for about 1 to 600 seconds. Is preferred. Moreover, when the said plastic base material consists of a material which is easy to cause a deformation | transformation and discoloration by heating, it is preferable to cure at a comparatively low temperature of about 30-100 degreeC.

  Although the film thickness of the coating film formed using the coating agent for plastic substrates of the present invention can be appropriately adjusted according to the use of the substrate, it is usually about 0.5 μm to 20 μm. preferable.

  In addition, when obtaining a laminate having a coating film comprising a coating agent for forming a top layer on the coating film surface formed using the coating agent for a plastic substrate of the present invention on the substrate, Conventionally known acrylic resin-based paints, polyester resin-based paints, alkyd resin-based paints, epoxy resin-based paints, fatty acid-modified epoxy resin-based paints, silicone resin-based paints, polyurethane resin-based paints as top layer forming coating agents Etc. can be used.

  As described above, a laminate in which the plastic substrate and a coating film formed using the coating agent for a plastic substrate of the present invention are laminated includes, for example, mobile phones, home appliances, OA equipment, and automobile interiors. It can be used for the surface coating of plastic products constituting automobile parts such as exterior materials, parts of various home appliances, building material products and the like.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

Synthesis example 1 [Preparation example of condensate of methyltrimethoxysilane (a3′-1)]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 1421 parts by mass of methyltrimethoxysilane (MTMS) was charged and heated to 60 ° C.

  Next, a mixture of 0.17 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 207 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then 80 The mixture was stirred at a temperature of 4 ° C. for 4 hours to cause hydrolysis and condensation reaction.

  The condensate obtained by the hydrolysis-condensation reaction has a temperature of 40 to 60 ° C. and a reduced pressure of 300 to 10 mmHg (the reduced pressure condition at the start of the distillation of methanol is 300 mmHg, and finally the pressure is reduced to 10 mmHg). (Hereinafter the same shall apply)) to remove the methanol and water produced in the reaction process, thereby removing a mixed liquid (active ingredient) of methyltrimethoxysilane condensate (a3′-1) having a number average molecular weight of 1000 70 mass%) 1000 mass parts was obtained.

  In addition, with the said active ingredient, the theoretical yield (mass part) when all the methoxy groups of silane monomers, such as methyltrimethoxysilane (MTMS), carried out condensation reaction was remove | divided by the actual yield (mass part) after condensation reaction. It is calculated from the value [theoretical yield (mass part) when all methoxy groups of the silane monomer undergo a condensation reaction / actual yield (mass part) after the condensation reaction].

Synthesis Example 2 [Preparation Example of Condensate of Ethyltrimethoxysilane (a3′-2)]
Into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 1296 parts by mass of ethyltrimethoxysilane (ETMS) was charged and heated to 60 ° C.

  Next, a mixture of 0.14 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 171 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then 80 The mixture was stirred at 4 ° C. for 4 hours to cause hydrolysis and condensation reaction.

  The condensate obtained by the hydrolysis condensation reaction was distilled at a temperature of 40 to 60 ° C. and a reduced pressure of 300 to 10 mmHg to remove methanol and water, thereby removing ethyl trimethoxysilane having a number average molecular weight of 1100. 1000 parts by mass of a mixed solution (active ingredient 70% by mass) containing the condensate (a3′-2) was obtained.

Abbreviations in Table 1 are described below. “MTMS”: Methyltrimethoxysilane “ETMS”: Ethyltrimethoxysilane

Synthesis Example 3 [Preparation of Composite Resin Intermediate Containing Liquid (C-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 125 parts by mass of propylene glycol monopropyl ether (PnP), 168 parts by mass of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) ) 102 parts by mass were charged and heated to 80 ° C.

  Next, at the same temperature, 38 parts by mass of methyl methacrylate (MMA), 24 parts by mass of butyl methacrylate (BMA), 36 parts by mass of butyl acrylate (BA), 24 parts by mass of acrylic acid (AA), 3-methacryloxypropyltrimethoxysilane (MPTS) A mixture containing 4 parts by mass, 54 parts by mass of PnP and 6 parts by mass of tert-butylperoxy-2-ethylhexanoate (TBPEH) was dropped into the reaction vessel over 4 hours, and then the same. By reacting at a temperature for 2 hours, an acrylic polymer organic solvent solution (c1) having a number average molecular weight of 10200 having a carboxyl group and a hydrolyzable silyl group was obtained.

  Next, a mixture of 2.7 parts by mass of “A-3” [iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.] and 76 parts by mass of deionized water was added dropwise over 5 minutes, and further stirred at the same temperature for 1 hour. The hydrolytic condensation reaction of the acrylic polymer in the organic solvent solution (c1) and the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS A composite resin intermediate containing liquid (C′-1) was obtained.

  Next, the composite resin intermediate-containing liquid (C′-1) and 291 parts by mass of the methyltrimethoxysilane condensate (a3′-1) are mixed, and 49 parts by mass of deionized water is added. By stirring at the same temperature for 16 hours to cause a hydrolysis condensation reaction, a condensate (a3′-1) of methyltrimethoxysilane was further bonded to the composite resin intermediate in the liquid containing (C′-1). 1000 mass parts of composite resin intermediate containing liquid (C-1) was obtained.

Synthesis Example 4 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-2)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 121 parts by mass of PnP, 267 parts by mass of PTMS and 162 parts by mass of DMDMS were charged and heated to 80 ° C.

  Next, at the same temperature, a mixture containing 61 parts by mass of MMA, 50 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 52 parts by mass of PnP and 6 parts by mass of TBPEH was dropped into the reaction vessel over 4 hours. Then, the mixture was further reacted at the same temperature for 2 hours to obtain an organic solvent solution (c2) of an acrylic polymer having a carboxyl group and a hydrolyzable silyl group and a number average molecular weight of 10300.

  Next, a mixture of 4.3 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 1 hour. By carrying out hydrolytic condensation reaction, a composite resin-containing liquid (C′-) in which the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c2) and the polysiloxane derived from PTMS and DMDMS are combined. 2) 1000 mass parts was obtained.

  Next, 123 parts by mass of a methyltrimethoxysilane condensate (a3′-1) is added, 21 parts by mass of deionized water is further added, and the mixture is stirred at the same temperature for 16 hours. A composite resin intermediate-containing liquid (C-2) in which a condensate (a3′-1) of methyltrimethoxysilane was further bonded to the composite resin intermediate in the liquid containing (C′-2) was obtained.

Synthesis Example 5 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-3)]
Except for using 291 parts by mass of ethyltrimethoxysilane condensate (a3′-2) instead of 291 parts by mass of methyltrimethoxysilane condensate (a3′-1), the same method as in Synthesis Example 3, 1000 parts by mass of a composite resin intermediate containing liquid (C-3) in which the composite resin intermediate in the containing liquid (C'-1) and a condensate of ethyltrimethoxysilane (a3'-2) were combined were obtained. .

Synthesis Example 6 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-4)]
Stirrer, thermometer, dropping funnel, into a reaction vessel equipped with a cooling tube and a nitrogen gas inlet, PnP 129 parts by weight, were charged PTMS 283 parts by mass and DMDMS 171 parts by weight, and the temperature was raised to 80 ° C..

  Next, at the same temperature, a mixture containing 21 parts by mass of MMA, 13 parts by mass of BMA, 20 parts by mass of BA, 13 parts by mass of AA, 2.1 parts by mass of MPTS, 58 parts by mass of PnP and 3.5 parts by mass of TPEHE, An organic solvent solution of an acrylic polymer having a number average molecular weight of 9900 (c4) having a carboxyl group and a hydrolyzable silyl group by allowing the reaction vessel to drop in 4 hours and further reacting at the same temperature for 2 hours. Got.

  Next, a mixture of 4.6 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 129 parts by mass of deionized water was added dropwise over 5 minutes, and further stirred at the same temperature for 1 hour. Then, a hydrolytic condensation reaction is performed, whereby the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c4) and the polysiloxane derived from PTMS and DMDMS are combined (C ′ -4) 1000 mass parts was obtained.

  Next, the composite resin intermediate (C′-4) and 130 parts by mass of the methyltrimethoxysilane condensate (a3′-1) are mixed, and further 22 parts by mass of deionized water is added at the same temperature. The composite resin intermediate-containing liquid in which a methyltrimethoxysilane condensate (a3′-1) is further bonded to the composite resin intermediate (C′-4) by stirring for 16 hours at a hydrolytic condensation reaction. (C-4) was obtained.

Example 1 [Preparation of coating agent (I) for plastic substrate]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries, Ltd.) 158 in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet. Part by mass and 66 parts by mass of isophorone diisocyanate (IPDI) were added, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 13 parts by mass of dimethylolpropionic acid (DMPA), 5 parts by mass of neopentyl glycol (NPG), and 121 parts by mass of methyl ethyl ketone (MEK) were added into the reaction vessel, and then further The reaction was carried out at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 30 parts by mass of 3-aminopropyltriethoxysilane (APTES) and 285 parts by mass of isopropyl alcohol (IPA) are put into the reaction vessel to cause a reaction with a carboxyl group. An organic solvent solution (i) of polyurethane having a number average molecular weight of 7400 having a functional silyl group was produced.

  Next, the total amount of the organic solvent solution (i) of polyurethane and 158 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed, and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring. Liquid containing composite resin in which hydrolyzable silyl group possessed by polyurethane in organic solvent solution (i) and hydrolyzable silyl group possessed by composite resin intermediate in said containing liquid (C-1) are combined ( I ').

  Next, a neutralized product obtained by neutralizing carboxyl groups in the composite resin is obtained by mixing the composite resin-containing liquid (I ′) and 10 parts by mass of triethylamine (TEA), and then the neutralized product and A mixture of an organic solvent and 610 parts by weight of deionized water is distilled under reduced pressure of 300 to 10 mmHg for 4 hours under the condition of 40 to 60 ° C. to remove the generated methanol, organic solvent and water. Thus, 1000 parts by mass of a coating material (I) for a plastic substrate having a nonvolatile content of 35.0% by mass was obtained.

  Table 2 shows mass ratios of [polysiloxane structure / composite resin] and [vinyl polymer structure / hydrophilic group-containing polyurethane structure] of the composite resin in the obtained coating material for plastic substrates.

Example 2 [Preparation of coating agent (II) for plastic substrate]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, a polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries Ltd.) 142 Part by mass and 60 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 12 parts by mass of DMPA, 4 parts by mass of NPG, and 110 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature was lowered to 50 ° C., and 27 parts by mass of APTES and 258 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (ii) was obtained.

  Next, the total amount of the organic solvent solution (ii) of polyurethane and 209 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed, and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring, Liquid containing composite resin (II) in which hydrolyzable silyl group of polyurethane in organic solvent solution (ii) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined ') Got.

  Next, the composite resin-containing liquid (II ′) and 13 parts by mass of TEA were mixed to obtain a neutralized product in which the carboxyl groups in the composite resin were neutralized. Next, the neutralized product and the organic solvent By distilling a mixture of the mixture and 610 parts by mass of deionized water under the same conditions as in Example 1, 1000 parts by mass of the coating material for plastic substrate (II) having a nonvolatile content of 35.0% by mass was obtained. Obtained.

Example 3 [Preparation of coating agent (III) for plastic substrate]
Example 2 with the exception of using 216 parts by mass of composite resin intermediate (C-2) instead of 209 parts by mass of composite resin intermediate (C-1) and 7 parts by mass of TEA instead of 13 parts by mass of TEA In the same manner, 1000 parts by mass of a coating material (III) for a plastic substrate having a nonvolatile content of 35.1% by mass was obtained.

Example 4 [Preparation of coating agent (IV) for plastic substrate]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries, Ltd.) having a 1,6-hexanediol skeleton in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser, and a nitrogen gas inlet 123 A mass part and 50 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 10 parts by mass of DMPA, 4 parts by mass of NPG, and 94 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature was lowered to 50 ° C., and 23 parts by mass of APTES and 221 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7300 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (iv) was obtained.

  Next, the total amount of the organic solvent solution (iv) of polyurethane and 279 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring. Liquid containing composite resin (IV ′) in which hydrolyzable silyl group of polyurethane in solvent solution (iv) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined Got.

  Next, by mixing 14 parts by mass of the composite resin-containing liquid (IV ′) and TEA, a neutralized product obtained by neutralizing the carboxyl group in the composite resin was obtained. A mixture of a solvent and 610 parts by weight of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts by weight of a coating agent (IV) for a plastic substrate having a nonvolatile content of 35.0% by weight. Got a part.

Example 5 [Preparation of coating agent (V) for plastic substrate]
Implemented except that 288 parts by mass of composite resin intermediate containing liquid (C-2) was used instead of 279 parts by mass of composite resin intermediate containing liquid (C-1) and 6 parts by mass of TEA was used instead of 14 parts by mass of TEA In the same manner as in Example 4, 1000 parts by mass of the coating material for plastic substrate (V) having a nonvolatile content of 35.1% by mass was obtained.

Example 6 [Preparation of coating agent (VI) for plastic substrate]
A plastic group having a nonvolatile content of 35.1% by mass in the same manner as in Example 4 except that 279 parts by mass of the composite resin intermediate (C-1) was used instead of 279 parts by mass of the composite resin intermediate (C-1). 1000 parts by mass of the coating agent (VI) for the material was obtained.

Example 7 [Preparation of coating agent (VII) for plastic substrate]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries, Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet 61 Part by mass and 26 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 5 parts by mass of DMPA, 2 parts by mass of NPG, and 47 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 12 parts by mass of APTES and 110 parts by mass of IPA are introduced into the reaction vessel and reacted to form a polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group. An organic solvent solution (vii) was obtained.

  Next, the total amount of the organic solvent solution (vii) of polyurethane and 489 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed, and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring, Liquid containing composite resin in which hydrolyzable silyl group of polyurethane in organic solvent solution (vii) and hydrolyzable silyl group of composite resin intermediate in said containing liquid (C-1) are combined (VII ′ )

  Subsequently, the composite resin containing liquid (VII ′) and 16 parts by mass of TEA were mixed to obtain a neutralized product in which the carboxyl group in the composite resin was neutralized, and then the neutralized product and the organic solvent. A mixture of the mixture and 560 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of the coating material for plastic substrate (VII) having a nonvolatile content of 35.0% by mass. Obtained.

Comparative Example 1 (Preparation of Comparative Plastic Substrate Coating Agent (VIII))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 60 parts by mass of PnP, 365 parts by mass of MTMS and 32 parts by mass of DMDMS were charged and heated to 80 ° C.

  Next, 93 parts by mass of MMA, 53 parts by mass of BA, 27 parts by mass of MPTS, 7 parts by mass of AA, 20 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA), 10 parts by mass of PnP, and 10 parts by mass of TBPEH at the same temperature. The mixture containing the acrylic polymer having a number average molecular weight of 16000 having a carboxyl group and a hydrolyzable silyl group is further dropped for 2 hours at the same temperature after dropping into the reaction vessel over 4 hours. An organic solvent solution (viii) was obtained.

  Next, in a reaction vessel containing the organic solvent solution (viii) of the acrylic polymer, 4.6 parts by weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 154 parts by weight of deionized water. The mixture was added dropwise to the hydrolyzable silyl group possessed by the acrylic polymer in the organic solvent solution (viii) by adding the mixture to the hydrolyzed silyl group in the organic solvent solution (viii). A liquid (VIII ′) containing a composite resin for comparison to which a polysiloxane derived from DMDMS was bonded was obtained.

  Next, the neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin was obtained by mixing the comparative composite resin-containing liquid (VIII ′) and 21 parts by mass of TEA. A mixture of an organic solvent and a mixture of organic solvents and 530 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain a coating agent for a comparative plastic substrate having a non-volatile content of 40.3% by mass. (VIII) 1000 parts by mass were obtained.

Comparative Example 2 (Preparation of Comparative Plastic Base Coating Agent (IX))
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet was charged with 36 parts by mass of PnP, 80 parts by mass of IPA, 32 parts by mass of PTMS, and 19 parts by mass of DMDMS, and the temperature was raised to 80 ° C. Warm up.

  Next, at the same temperature, a mixture containing 9 parts by mass of MMA, 86 parts by mass of BMA, 67 parts by mass of BA, 14 parts by mass of MPTS, 16 parts by mass of AA, 14 parts by mass of PnP, and 14 parts by mass of TBPEH was added to the reaction vessel. After dropwise addition to 4 hours, the mixture was further reacted at the same temperature for 2 hours to obtain an organic solvent solution (ix) of an acrylic polymer having a carboxyl group and a hydrolyzable silyl group and having a number average molecular weight of 13100.

  Next, in a reaction vessel containing the organic solvent solution (ix) of the acrylic polymer, 0.9 part by mass of “A-3” [iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.] and 24 parts by mass of deionized water. Is added dropwise over 5 minutes, and is further stirred for 10 hours at 80 ° C. to cause a hydrolytic condensation reaction, whereby the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (ix) is obtained. A liquid (IX ′) containing a comparative composite resin to which polysiloxane derived from PTMS and DMDMS were bonded was obtained.

  Subsequently, the neutralized material which neutralized the carboxyl group in the said composite resin for a comparison was obtained by mixing 18 mass parts of TEA containing liquid (IX ') of the said composite resin for a comparison, and then this neutralized material And a mixture of an organic solvent and 124 parts by mass of a condensate of methyltrimethoxysilane (a3′-1) are mixed with 550 parts by mass of deionized water and distilled under the same conditions as in Example 1. As a result, 1000 parts by mass of the coating agent (IX) for comparative plastic substrate having a nonvolatile content of 40.0% by mass was obtained.

Comparative Example 3 [Preparation of Comparative Plastic Substrate Coating Agent (X)]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries Co., Ltd.) 171 in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet. Part by mass and 72 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 14 parts by mass of DMPA, 5 parts by mass of NPG, and 132 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

Subsequently, the temperature is lowered to 50 ° C., and 33 parts by mass of APTES and 309 parts by mass of IPA are charged into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group is 7,500. Next, the total amount of the polyurethane organic solvent solution (x) was mixed with 112 parts by mass of the composite resin intermediate-containing liquid (C-1), and the mixture was stirred at 80 ° C. The liquid containing the comparative composite resin (X ′) in which the polyurethane in the organic solvent solution (x) and the composite resin intermediate in the containing liquid (C-1) are bonded together by hydrolytic condensation reaction for 1 hour. )

  Next, a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin (X ′) by mixing the comparative composite resin-containing liquid (X ′) with 12 parts by mass of TEA, By mixing a mixture of the neutralized product and organic solvent and 610 parts by mass of deionized water under the same conditions as in Example 1, a coating for a plastic substrate having a nonvolatile content of 35.0% by mass is obtained. 1000 mass parts of agent (X) was obtained.

Comparative Example 4 [Preparation of Comparative Plastic Base Coating Agent (XI)]
Polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries, Ltd.) having a 1,6-hexanediol skeleton in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser, and nitrogen gas inlet 187 A mass part and 78 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 15 parts by mass of DMPA, 6 parts by mass of NPG, and 144 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

Next, the temperature was lowered to 50 ° C., and 36 parts by mass of APTES and 339 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (xi) was obtained.
Next, the total amount of the polyurethane organic solvent solution (xi) and 56 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed, and the mixture is subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring. A comparative composite resin containing liquid (XI ′) in which the polyurethane in the solvent solution (xi) and the composite resin intermediate in the containing liquid (C-1) were bonded together was obtained.

  Next, by mixing the composite resin-containing liquid (XI ′) and 11 parts by mass of TEA, a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin was obtained, and then the neutralized product and A mixture of an organic solvent and 610 parts by mass of deionized water is distilled under the same conditions as in Example 1 to obtain a coating agent (XI) 1000 for a plastic substrate having a non-volatile content of 35.0% by mass. A mass part was obtained.

Comparative Example 5 [Preparation Example of Coating Agent for Plastic Base for Comparison (XII)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen gas inlet, a polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries, Ltd.) 27 Part by mass and 11 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 2 parts by mass of DMPA, 1 part by mass of NPG, and 144 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

Next, the temperature was lowered to 50 ° C., and 5 parts by mass of APTES and 49 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (xii) was obtained.
Next, the whole amount of the organic solvent solution (xii) of polyurethane and 676 parts by mass of the composite resin intermediate-containing solution (C-1) are mixed and subjected to a hydrolysis-condensation reaction at 80 ° C. for 1 hour with stirring. A comparative composite resin containing liquid (XII ′) in which the polyurethane in the solvent solution (xii) and the composite resin intermediate in the containing liquid (C-1) were combined was obtained.

  Next, by mixing the composite resin-containing liquid (XII ′) and 12 parts by mass of TEA, a neutralized product in which the carboxyl group in the comparative composite resin was neutralized was obtained, and then the neutralized product and A mixture of an organic solvent and 610 parts by mass of deionized water is distilled under the same conditions as in Example 1 to obtain a coating material for plastic substrate (XII) 1000 having a nonvolatile content of 35.0% by mass. A mass part was obtained.

Comparative Example 6 [Preparation Example of Coating Material for Comparative Plastic Substrate (XIII)]
In a reaction container similar to that of Synthesis Example 1, 150 parts by mass of PnP was charged and heated to 80 ° C.

  Next, a mixture containing 60 parts by mass of MMA, 45 parts by mass of BMA, 57 parts by mass of BA, 38 parts by mass of AA, 50 parts by mass of PnP, and 9 parts by mass of TBPEH at the same temperature was added into the reaction vessel over 4 hours. After the dropwise addition, the mixture was further reacted at the same temperature for 2 hours to obtain an acrylic polymer (xiii-1) having a carboxyl group and a number average molecular weight of 16000.

  In another reaction container similar to Synthesis Example 1, 260 parts by mass of polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries, Ltd.) and 110 parts by mass of IPDI Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature is lowered to 80 ° C., and 22 parts by mass of DMPA, 8 parts by mass of NPG, and 400 parts by mass of MEK are put into the reaction vessel, and further reacted at 80 ° C. for 5 hours, thereby having a carboxyl group. A polyurethane (xiii-2) having a number average molecular weight of 7,600 was obtained.

  By mixing 109 parts by mass of the above-mentioned acrylic polymer (xiii-1), 656 parts by mass of polyurethane (xiii-2), and 235 parts by mass of the condensate of methyltrimethoxysilane (a3′-1), a plastic substrate is used. 1000 parts by mass of the coating agent (XIII) was obtained.

Example 8 [Preparation of coating agent for plastic substrate (XIV)]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries, Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet 61 First, 61 parts by mass of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 51 parts by mass of isophorone diisocyanate (IPDI) were added, the temperature was raised to 100 ° C., and the same temperature was maintained for 1 hour Reacted.

  Subsequently, the temperature was lowered to 80 ° C., 10 parts by mass of dimethylolpropionic acid (DMPA), 4 parts by mass of neopentyl glycol (NPG), and 94 parts by mass of methyl ethyl ketone (MEK) were added into the reaction vessel. The reaction was carried out at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 23 parts by mass of 3-aminopropyltriethoxysilane (APTES) and 221 parts by mass of isopropyl alcohol (IPA) are put into the reaction vessel and reacted, thereby hydrolyzing the carboxyl group. An organic solvent solution (xiv) of polyurethane having a number-average molecular weight of 7300 having a functional silyl group was produced.

  Next, the whole amount of the organic solvent solution (xiv) of polyurethane and 279 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed and subjected to a hydrolysis condensation reaction at 80 ° C. for 1 hour with stirring. Liquid containing composite resin in which hydrolyzable silyl group possessed by polyurethane in organic solvent solution (xiv) and hydrolyzable silyl group possessed by composite resin intermediate in said containing liquid (C-1) are combined ( XIV ') was obtained.

  Next, a neutralized product obtained by neutralizing the carboxyl group in the composite resin is obtained by mixing the composite resin-containing liquid (XIV ′) and 7 parts by mass of triethylamine (TEA), and then the neutralized product and A mixture of an organic solvent and 610 parts by weight of deionized water is distilled under reduced pressure of 300 to 10 mmHg for 4 hours under the condition of 40 to 60 ° C. to remove the generated methanol, organic solvent and water. Thus, 1000 parts by mass of a coating agent for plastic substrate (XIV) having a nonvolatile content of 35.0% by mass was obtained.

Example 9 [Preparation of coating agent for plastic substrate (XV)]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200 manufactured by Ube Industries, Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet 61 1 part by mass, 61 parts by mass of polyester polyol (polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid, hydroxyl group equivalent 1000 g / equivalent), 51 parts by mass of isophorone diisocyanate (IPDI) The mixture was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 10 parts by mass of dimethylolpropionic acid (DMPA), 4 parts by mass of neopentyl glycol (NPG), and 94 parts by mass of methyl ethyl ketone (MEK) were added into the reaction vessel. The reaction was carried out at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 23 parts by mass of 3-aminopropyltriethoxysilane (APTES) and 221 parts by mass of isopropyl alcohol (IPA) are put into the reaction vessel and reacted, thereby hydrolyzing the carboxyl group. An organic solvent solution (xv) of polyurethane having a number average molecular weight of 7300 having a functional silyl group was produced.

  Next, the total amount of the organic solvent solution (xv) of polyurethane and 279 parts by mass of the composite resin intermediate-containing liquid (C-1) are mixed, and subjected to a hydrolysis condensation reaction at 80 ° C. for 1 hour with stirring. Liquid containing composite resin in which hydrolyzable silyl group possessed by polyurethane in organic solvent solution (xiv) and hydrolyzable silyl group possessed by composite resin intermediate in said containing liquid (C-1) are combined ( XV ').

  Next, a neutralized product obtained by neutralizing the carboxyl group in the composite resin is obtained by mixing the composite resin-containing liquid (XV ′) and 7 parts by mass of triethylamine (TEA), and then the neutralized product and A mixture of an organic solvent and 610 parts by weight of deionized water is distilled under reduced pressure of 300 to 10 mmHg for 4 hours under the condition of 40 to 60 ° C. to remove the generated methanol, organic solvent and water. Thus, 1000 parts by mass of a coating agent for plastic substrate (XV) having a nonvolatile content of 35.0% by mass was obtained.

  The storage stability described in Tables 2 to 4 shows the viscosity (initial viscosity) of the plastic substrate coating agent and the viscosity after leaving the plastic substrate coating agent in a 50 ° C. environment for 30 days ( The viscosity with time was measured and evaluated by the value obtained by dividing the viscosity with time by the initial viscosity [viscosity with time / initial viscosity]. If the value is about 0.5 to 3.0, it can be used as a paint.

  The [polysiloxane structure / composite resin] and [vinyl polymer (a2) structure / hydrophilic group-containing polyurethane (a1) structure] are based on the ratio of raw materials used in the production of the composite resin (A). Asked. The mass ratio of [polysiloxane structure / composite resin] was calculated in consideration of the formation of by-products such as methanol and ethanol that can be generated when the polysiloxane structure is formed.

  Various physical properties of the coating film comprising the above-mentioned coating agents for plastic substrates (I) to (VII) and (XIV) to (XV) and comparative plastic substrate coating agents (VIII) to (XIII) are as follows. Evaluation was performed according to the evaluation method.

  In addition, various curing agents are added to the plastic base coating agents (I) to (VII) and (XIV) to (XV) and the comparative plastic base coating agents (VIII) to (XIII). Various physical properties of the coating film made of each coating material for plastic substrates obtained by mixing according to the blending composition described in 9 were also evaluated according to the following evaluation methods.

The following curing agents were used.
“GPTMS”; 3-glycidoxypropyltrimethoxysilane “MS-51”; “MKC silicate MS-51” manufactured by Mitsubishi Chemical Corporation (polymethoxysiloxane having a condensation degree of 2 to 9)

[Durability of coating film (solvent resistance, acid resistance), weather resistance evaluation method]
<Method for producing test plate>
On the polycarbonate (PC) substrate manufactured by Engineering Test Service Co., Ltd., the above-mentioned coating agent for plastic substrate is applied so as to have a dry film thickness of 10 μm and dried at 80 ° C. for 20 minutes. A test plate (1) in which a coating film was laminated on a substrate was obtained.

<Durability (solvent resistance) evaluation method>
Using the felt soaked with methyl ethyl ketone, the same portion of the surface of the test plate (1) was rubbed back and forth 50 times. The state of the coating film before rubbing and after rubbing was confirmed by finger touch and visual observation, and evaluated according to the following evaluation criteria.

○: Softening and gloss reduction are not observed before and after rubbing.
Δ: Some softening or gloss reduction is observed before and after rubbing.
X: Significant softening or gloss reduction is observed before and after rubbing.

  In addition, the thing for which the said coating agent for plastic base materials did not contact | adhere to the said base material surface but was not able to produce a test board did not perform the solvent resistance evaluation test. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

<Durability (acid resistance) evaluation method>
After leaving the surface of the test plate (1) immersed in a 5% by mass sulfuric acid aqueous solution for 24 hours at a temperature of 25 ° C., the coating film was washed with water and then the surface condition of the dried coating film was visually observed. It confirmed and evaluated according to the following evaluation criteria.

○: There is no etching mark.
Δ: There is a slight etching mark.
X: Remarkable etching.

  In addition, the acid-resistant evaluation test was not performed for the plastic substrate coating agent that did not adhere to the substrate surface and could not produce a test plate. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

<Evaluation method of weather resistance>
Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 60 ° C., wetting: humidity 90% or more, 40 ° C., light irradiation / wetting cycle = 4 hours / 4 hours] and 1000 hours exposure test.

  Here, the specular gloss reflectance of the surface coating film of the test plate before and after the exposure test was measured using HG-268 manufactured by Suga Test Instruments Co., Ltd., and the gloss retention was determined based on the following formula. .

  [100 × (specular reflectance of coating film after exposure test) / (specular reflectance of coating film before exposure test)] The greater the gloss retention value, the better the weather resistance. % Or more is preferable.

  In addition, the evaluation test of a weather resistance was not performed for the plastic substrate coating agent that did not adhere to the substrate surface and could not produce a test plate. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Adhesion evaluation method]
The coating agent for plastic substrate is made of a polycarbonate (PC) substrate, a polyethylene terephthalate (PET) substrate, an acrylonitrile-butadiene-styrene (ABS) substrate, polymethyl methacrylate (PMMA) manufactured by Engineering Test Service Co., Ltd. ) On a base material, a polystyrene (PS) base material, a polyvinyl chloride (PVC) base material, and a 6-nylon (NR) base material, it was applied to a dry film thickness of 10 μm and dried at 80 ° C. for 20 minutes. Thus, a test plate having a coating film laminated on each plastic substrate was produced.

  The adhesion of the coating film formed on the surface of the test plate to the plastic substrate was evaluated according to JIS K-5400 cross-cut test method. The evaluation criteria are as follows.

A: No peeling of the coating film was observed.
○: The peeled area of the coating film was less than 30% of the total grid area.
(Triangle | delta): The area where the coating film peeled was 30 to less than 95% of the total grid area.
X: The area where the coating film peeled was 95% or more of the total grid area.

[Evaluation method 1 of substrate followability (elongation)]
The substrate followability of the coating film was evaluated based on the elongation and crack resistance of the coating film.

  First, the plastic substrate coating agent is applied on a substrate made of polypropylene film so that the film thickness becomes 200 μm, dried in an environment of 140 ° C. for 5 minutes, and further in an environment of 25 ° C. What dried for 24 hours and peeled from this base material was made into the test coating film (10 mm x 70 mm).

  For the measurement of the elongation of the test coating film, Autograph AGS-1kNG manufactured by Shimadzu Corporation (distance between chucks: 20 mm, pulling speed: 300 mm / min., Measurement atmosphere: 22 ° C., 60% RH) was used. And evaluated based on the elongation percentage with respect to the coating film before the tensile test. It is practically preferable that the elongation is approximately 80% or more.

[Evaluation Method 2 for Substrate Followability (Crack Resistance)]
Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 60 ° C., wetting: humidity 90% or more, 40 ° C., light irradiation / wetting cycle] = 4 hours / 4 hours], the appearance of the coating film on the surface of the test plate was visually evaluated according to the following evaluation criteria.

○: No cracks are observed on the coating surface.
Δ: Some cracks are observed on a very small part of the coating film surface.
X: Generation | occurrence | production of a crack is seen in the whole coating-film surface.

  In addition, the thing which the coating agent for plastic base materials did not adhere | attach on the said base material surface but was not able to produce a test board did not perform the evaluation test of crack resistance. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Contamination resistance evaluation method]
The test plate (1) was subjected to an exposure test for 3 months in DIC Corporation Sakai Factory in Takaishi City, Osaka Prefecture.

  Here, the color difference (ΔE) between the unwashed test coating film after the exposure test and the test coating film before the exposure test was evaluated using CM-3500d manufactured by Konica Minolta Sensing Co., Ltd. The smaller the color difference (ΔE), the better the stain resistance.

Explanation of Abbreviations in Tables “PC plate”: Polycarbonate plate “PET plate”: Polyethylene terephthalate plate “ABS plate”: Acrylonitrile-butadiene-styrene plate “PMMA plate”: Polymethyl methacrylate plate “PS plate”: Polystyrene plate “ "PVC board": Polyvinyl chloride board "NR board": 6-nylon board

Claims (10)

The hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) are combined with a composite resin (A) bonded via a polysiloxane (a3) and an aqueous medium, and the hydrophilic group-containing polyurethane ( the bond between a1) and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) and a hydrolyzable silyl group of the polysiloxane (a3); And / or a bond between the vinyl polymer (a2) and the polysiloxane (a3) is formed by a reaction with a silanol group, and the hydrolyzable silyl group of the vinyl polymer (a2) and It is formed by the reaction of silanol groups with hydrolyzable silyl groups and / or silanol groups of the polysiloxane (a3). The polysiloxane (a3) is a polysiloxane (a3-1) having at least one structure selected from the group consisting of the following general formulas (I) and (II), and the alkyl group has 1 carbon atom. -3 alkyltrialkoxysilane condensate (a3-2) is bonded via a bond between a silicon atom and an oxygen atom, and the structure derived from the polysiloxane (a3) is a composite resin. (A) The coating agent for plastic substrates characterized by being contained in 15-55 mass% with respect to the whole.

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ] The coating agent for plastic substrates according to claim 1, wherein the hydrophilic group-containing polyurethane (a1) has a structural unit derived from polycarbonate polyol. The plastic according to claim 1, wherein a mass ratio [(a2) / (a1)] of the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) is in a range of 20/1 to 1/20. Substrate coating agent. The vinyl polymer (a2) is obtained by polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer. The coating agent for plastic substrates according to claim 1, wherein The polysiloxane (a3) has an aromatic cyclic structure bonded to a silicon atom, an alkyl group having 1 to 3 carbon atoms bonded to a silicon atom, and 1 to 3 carbon atoms bonded to a silicon atom. The coating agent for plastic substrates of Claim 1 which has 1 or more types chosen from the group which consists of the alkoxy group which has. A coating agent for coating a surface of a transparent plastic substrate, comprising the coating agent for a plastic substrate according to any one of claims 1 to 5 . Selected from the group consisting of polycarbonate base, polyester base, acrylonitrile-butadiene-styrene base, polyacryl base, polystyrene base, polyurethane base, epoxy resin base, polyvinyl chloride base and polyamide base the surface of the plastic substrate to, claim 1 laminate having a coating film formed by using a plastic substrate for a coating agent according to any one of 5. The laminated body which has the coating film formed on the surface of organic glass using the coating agent for plastic base materials in any one of Claims 1-5 . The member for motor vehicles by which the coating film formed using the coating agent for plastic substrates in any one of Claims 1-5 was laminated | stacked on the surface of organic glass. A method for producing a coating material for a plastic substrate comprising the following steps (1) to (4) , wherein the coating material for a plastic substrate comprises a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2): And a composite resin (A) bonded via a polysiloxane (a3) and an aqueous medium, and the bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) is The hydrolyzable silyl group and / or silanol group possessed by the hydrophilic group-containing polyurethane (a1) and the hydrolyzable silyl group and / or silanol group possessed by the polysiloxane (a3) are formed, And the bond between the vinyl polymer (a2) and the polysiloxane (a3) is a hydrolyzable silyl group and the vinyl polymer (a2). / Or is formed by a reaction between a hydrolyzable silyl group and / or a silanol group of the polysiloxane (a3), and the polysiloxane (a3) is represented by the following general formulas (I) and ( II) and a polysiloxane (a3-1) having at least one structure selected from the group consisting of II) and an alkyltrialkoxysilane condensate (a3-2) having 1 to 3 carbon atoms in the alkyl group, It is bonded via a bond between an atom and an oxygen atom, and the structure derived from the polysiloxane (a3) is included in the range of 15 to 55% by mass with respect to the entire composite resin (A). A method for producing a coating material for a plastic substrate .

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ]
(1) By polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer in the presence of an organic solvent, A step of obtaining an organic solvent solution of the combined (a2),
(2) The polysiloxane (a3) is bonded to the vinyl polymer (a2) by reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2). A step of obtaining an organic solvent solution of the obtained resin (C),
(3) The resin (C) and the hydrophilic group-containing polyurethane (a1) having a hydrolyzable silyl group and / or silanol group are mixed, and the polysiloxane (a3) in the resin (C) has. By reacting the hydrolyzable silyl group and / or silanol group with the hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) , the vinyl polymer (a2) and the hydrophilic group are made hydrophilic. A step of obtaining an organic solvent solution of the composite resin (A) in which the group-containing polyurethane (a1) is bonded via the polysiloxane (a3);
(4) The hydrophilic group of the composite resin (A) in the organic solvent is neutralized, and the neutralized product is mixed into the aqueous medium by mixing the organic solvent solution containing the neutralized product with the aqueous medium. The process of dissolving or dispersing.