JP5661844B2 - Coating composition, cured film and resin laminate - Google Patents

Description

  The present invention relates to a transparent cured film, a coating composition, and a resin laminate subjected to a surface treatment with this composition.

  Thermoplastics, particularly polycarbonate resins, are widely used as structural materials to replace glass because they are excellent in transparency, lightweight and excellent in impact resistance. However, since the surface properties such as scratch resistance, weather resistance and chemical resistance are inferior, the use thereof is limited, and there is a strong demand for improving the surface properties of the polycarbonate resin substrate.

  As a method for improving the surface characteristics, there is a method of coating the surface of a polycarbonate resin molded article with a surface treatment agent. For example, a method has been proposed in which a cured layer made of a polyfunctional acrylic photocurable resin or a melamine-based or organopolysiloxane-based thermosetting resin is formed on the surface of a polycarbonate resin substrate.

  Of these, those coated with organosiloxane are considered useful because they are excellent in scratch resistance and chemical resistance. However, the coating with the organosiloxane resin has a problem in adhesion to the polycarbonate resin, and particularly has a problem that the coating layer is peeled off when used outdoors for a long period of time. Further, in order to improve adhesion and wear resistance, there is a problem that even if the thickness of the organosiloxane resin is increased, there is a problem that cracks are likely to occur at the time of curing, and improvement is desired.

  Regarding the improvement of adhesion, Patent Document 1 proposes a method of blending various polymers having good adhesion to paints and hard coat materials, but the scratch resistance is insufficient. In addition, when an organic solvent such as toluene or tetrahydrofuran (THF) is used to dissolve the polymer, the surface of the polycarbonate substrate or the like is affected, so that it is difficult to form a transparent laminate. In some cases, the weather resistance of the paint or hard coat material is significantly reduced. Therefore, in applications requiring scratch resistance and weather resistance, an acrylic or urethane paint containing an ultraviolet absorber is applied as a primer on a polycarbonate resin substrate, and a coating layer is further applied thereon. A two-coat system is common (Patent Document 2). However, since the work process is long, there is a problem in productivity, and development of a one-coat method is eagerly desired.

  Patent Document 3 proposes a technique for forming a thermosetting film with a single coat on a polycarbonate resin from an aqueous emulsion and colloidal silica, but the silica particles are dispersed inside the organic film formed by fusing organic fine particles. The formed film is formed. Although it is possible to impart adhesion to the resin substrate, it is difficult to impart wear resistance because the surface layer is formed of organic fine particles.

  Patent Document 4 proposes a method for realizing scratch resistance and adhesion by a one-coat method. In this method, a cured layer is provided on a polycarbonate resin substrate using at least one of an epoxy group-containing silane coupling agent and an amino group silane coupling agent as an silane coupling agent together with alkoxysilane. However, since the cured layer does not contain a polymeric ultraviolet absorber, it cannot be said that the weather resistance is sufficient.

  Patent Document 5 discloses a composition containing a silicone-containing polymeric ultraviolet absorber and polyorganosiloxane. However, the dispersion cannot be stabilized only by mixing the polymer ultraviolet absorber and the polyorganosiloxane.

  Patent Document 6 discloses a transparent cured film having an in-film structure in which polymer nanoparticles having ultraviolet absorbing ability are highly dispersed in silica. Although this transparent cured film is excellent in wear resistance, ultraviolet blocking performance and initial adhesion, there is room for improvement in terms of durability (boiling resistance).

JP 11-043646 A JP 2004-131549 A JP 2003-82272 A JP 2000-272071 A JP 2004-1393 A WO2006 / 022347 pamphlet

An object of the present invention is a cured film having good adhesion to a resin base material such as polycarbonate without using a primer, and having boiling resistance as a measure of excellent scratch resistance, weather resistance and durability. It is to provide a coating composition and a resin laminate.
Another object of the present invention is to provide a method for producing the cured film, the coating composition, and the resin laminate.

According to the present invention, the following cured film, coating composition, resin laminate and the like are provided.
1. Organic fine particles having an average particle diameter of 1 to 200 nm containing ultraviolet absorbing groups are dispersed in a matrix having a Si—O bond, visible light transmittance is 80% or more, and haze value is 10% or less. A cured film having boiling resistance.
2. 2. The cured film according to 1, wherein the volume fraction of the organic fine particles in the cured film is 0.5 to 70% by volume.
3. The curing in terms of SiO ₂ by weight of Si derived component contained in the film, the cured film according to 1 or 2 which is 30 to 80 wt% of the total weight of the cured film.
4). A coating composition comprising the following components (1) to (7).
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Blocked isocyanate silane compound (5) Polymer ultraviolet absorber (6) Curing catalyst (7) Solvent 5 . 5. Coating composition of 4 whose compounding quantity of said component (1)-(7) is the following range.
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound:
10-80% by weight
(2) Aminosilane compound: 1 to 60% by weight
(3) Epoxysilane compound: 1 to 60% by weight
(4) Blocked isocyanate silane compound: 1 to 60% by weight
(5) Polymer ultraviolet absorber: 0.1 to 50% by weight
(6) Curing catalyst: 0.1 to 40% by weight
(7) Solvent: 5 to 1000 parts by weight when the total of components (1) to (6) is 100 parts by weight. 6. The coating composition according to 4 or 5, wherein the curing catalyst is an organic acid.
A cured film obtained by curing the coating composition according to any one of 7.4 to 6.
The resin laminated body formed by forming the cured film in any one of 8.1-3 and 7 on the resin base material.
9. The manufacturing method of the coating composition prepared by mixing the following component (1)-(7).
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Blocked isocyanate silane compound (5) Polymer ultraviolet absorber (6) Curing catalyst (7) Solvent 10 . Producing a first mixed liquid containing at least component (1) and component (4);
10. The method for producing a coating composition according to 9, wherein the component (2) is finally mixed.
The manufacturing method of the cured film including the process of heating and hardening the coating composition in any one of 11.4-6.

  According to the present invention, a cured film having good adhesion to a resin base material such as polycarbonate without using a primer, and having boiling resistance as a measure of excellent scratch resistance, weather resistance and durability. A coating composition and a resin laminate can be provided.

  The cured film of the present invention is obtained by dispersing organic fine particles containing an ultraviolet absorbing group and having an average particle diameter of 1 to 200 nm in a matrix having a Si—O bond, and has a visible light transmittance of 80% or more. It has a haze value of 10 or less and has boiling resistance. By finely dispersing organic fine particles containing an ultraviolet absorbing group in the film, a cured film having excellent ultraviolet resistance and high transparency can be obtained.

The average particle diameter of the organic fine particles is preferably 100 nm or less. If the average particle size of the organic fine particles exceeds 200 nm, the transparency of the resin laminate may be lowered.
The average particle diameter of the organic fine particles means an average value obtained by observing a cross section of the thermosetting film on the resin substrate with a TEM (transmission electron microscope) and obtained by image processing software.
As the organic fine particles of the present invention, a polymeric ultraviolet absorber can be suitably used. The polymer ultraviolet absorber will be described later.
The particle component can be identified by elemental analysis using HAADF (High-angle tubular dark-field).

The visible light transmittance and haze value mean values for a cured film of 5 μm.
The visible light transmittance is a percentage of the total light quantity / visible light incident light quantity passing through the test piece. The haze value is the degree of an unclear cloudy appearance inside or on the surface of the transparent material. Scattered light transmittance / visible light transmittance in percentage.

  Boiling resistance is a performance that is a measure of the durability of a cured film. In the present invention, boiling resistance specifically refers to the cracking, change in appearance, and appearance of the cured film when the laminate having the cured film of the present invention formed on a substrate is immersed in boiling water for 1 hour. It means that there is no change in adhesion.

In the cured film of the present invention, the volume fraction of the organic fine particles in the cured film is preferably 0.5 to 70% by volume, more preferably 1 to 50% by volume. As a result, a cured film having high transparency and excellent ultraviolet absorption ability is obtained.
The volume fraction of the organic fine particles is obtained by observing the cross section of the thermosetting film on the resin substrate with a TEM (transmission electron microscope), obtaining the area% using image processing software, and calculating the value as “the thickness of the observation sample”. It means the value obtained by dividing by the “÷ average particle size” value.

Further, it the cured film of the present invention, in terms of the weight of SiO ₂ of Si derived component contained in the cured film is preferably 30 to 80 wt% of the total weight of the cured film is 35 to 75 wt% Is more preferable. By setting it within this range, a cured film having good film-forming properties (no cracks) and excellent scratch resistance can be obtained.
The converted weight of SiO ₂ was obtained by thermogravimetrically measuring a cured film sample formed on a Teflon (registered trademark) petri dish (20 ° C./minute temperature increase under nitrogen, room temperature to 800 ° C.), and the residue at 800 ° C. Obtained from the quantity value.

The cured film of the present invention can be applied to various resin substrates to form a resin laminate. Suitable for polycarbonate resins and polymethyl methacrylate (PMMA), and more preferred for polycarbonate resins.
The polycarbonate resin base material is not particularly limited, but from a bisphenol compound represented by 2,2-bis (4-hydroxyphenyl) alkane or 2,2-bis (4-hydroxy-3,5-dihalogenophenyl) alkane. A polymer produced by a known method is used, and the polymer skeleton may contain a structural unit derived from a fatty acid diol or a structural unit having an ester bond. Although it does not specifically limit about molecular weight, From a viewpoint of extrusion moldability or mechanical strength, the thing of 10,000-50,000 is preferable at a viscosity average molecular weight, and the thing of 13,000-40,000 is more preferable. Although there is no restriction | limiting in particular about the thickness of a base material, Preferably it is the range of about 0.1-20 mm. The polycarbonate resin substrate is preferably a transparent substrate.

  In addition, you may add suitably a ultraviolet absorber, antioxidant, a heat stabilizer, a flame retardant, an inorganic filler, an antistatic agent, a heat ray shielding agent, etc. in a resin base material as needed.

  In the case of a polycarbonate laminate, in order to further improve the weather resistance, 1 to 10 parts by weight, preferably 1 to 5 parts by weight of an ultraviolet absorber is preliminarily provided on the surface of the polycarbonate resin substrate with respect to 100 parts by weight of the polycarbonate resin. It is preferable to use a polycarbonate resin substrate provided with an added 5 to 100 μm polycarbonate resin layer. Examples of the ultraviolet absorber to be used include conventionally known benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, triazine-based, and the like. Generally, triazole-based is used.

  The method of providing the polycarbonate resin layer containing the ultraviolet absorber on the polycarbonate resin substrate is not particularly limited, but it is provided by a coextrusion method in which the polycarbonate resin and the polycarbonate resin containing the ultraviolet absorber are simultaneously melt extruded to form a sheet. It is preferable.

  In addition, although the resin laminated body of this invention is two layers of a resin base material and a coating layer, in the range which does not impair the effect of this invention, you may laminate | stack another layer suitably.

The cured film of the present invention can be prepared, for example, by curing the coating composition of the present invention described below.
The coating composition of the present invention includes the following components (1) to (7).
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Blocked isocyanate silane compound (5) Polymer ultraviolet absorber (6) Curing catalyst (7) Solvent

(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound The organoalkoxysilane compound (1) is an organoalkoxysilane compound containing no amino group, epoxy group, or isocyanate group. Bifunctional alkoxysilane and trifunctional alkoxysilane are preferred. Furthermore, a partial condensate (that is, a polyorganoalkoxysilane compound) in which these compounds are bonded by a siloxane bond (Si—O bond) can also be used. These compounds may be used alone or in combination of two or more.
Trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Tripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexylriboxysilane, decyltrimethoxysilane, decyltriethoxysilane Fluorinated alkyl (trialkoxy) silanes such as decyltripropoxysilane, decyltributoxysilane, and trifluoropropyltrimethoxysilane in which a fluorine atom is introduced into the substituent. Emissions, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane, and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are mentioned.
Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

A suitable organoalkoxysilane compound (1) can be represented by the following formula (1).
(R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ² is an alkyl group having 1 to 4 carbon atoms or an ether group, and m is an integer of 1 or 2.)

  Specific examples of the polyorganoalkoxysilane compound (1) include “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., and “AZ-” manufactured by Toray Dow Corning Co., Ltd. 6101 "," SR2402 "," AY42-163 ", and the like.

(2) Aminosilane Compound The aminosilane compound (amino group-containing silane compound) (2) is an alkoxysilane compound that contains an amino group but does not contain an epoxy group and an isocyanate group. Specific examples include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N -Methylaminopropyltriethoxysilane and the like.

A suitable aminosilane compound (2) can be represented by the following formula (2).
(R ¹¹ ) _n Si (OR ² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different, and the alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group (—NH ₂ group), aminoalkyl group (— (CH ₂ )) _x— NH ₂ ), an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups (—NHR groups), and at least one of R ¹¹ is an amino group, An alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group, wherein x in the aminoalkyl group is an integer of 1 to 3, and R in the alkylamino group is a carbon number. 1 to 3 alkyl groups, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

(3) Epoxysilane compound The epoxysilane compound (epoxy group-containing silane compound) (3) is an alkoxysilane compound that contains an epoxy group but does not contain an amino group and an isocyanate group. Specific examples include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

A suitable epoxysilane compound (3) can be represented by the following formula (3).
(R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

(4) Blocked isocyanate silane compound Blocked isocyanate silane compound (4) means that the isocyanate group is protected by a blocking agent such as oxime to be inactive, and is deblocked by heating to activate (regenerate) the isocyanate group. Isocyanate silane compound.
An isocyanate silane compound (isocyanate group-containing silane compound) is an alkoxysilane compound that contains an isocyanate group but does not contain an amino group or an epoxy group. Specific examples include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, isocyanate silane compounds, and the like. In the present invention, compounds in which isocyanate groups of these isocyanate silane compounds are blocked are used. The blocked isocyanate silane compound is preferably blocked isocyanate propyltriethoxysilane.

  Examples of isocyanate group blocking agents include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolaclam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol and n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl group such as ethyl lactate and amyl lactate Stealtes, mercaptans such as butyl mercaptan, hexyl mercaptan, acid amides such as acetanilide, acrylic amide, and timer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, 1 , 2,4-triazole and the like, and acid imides such as succinimide and phthalic imide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

(5) Polymer UV Absorber The polymer UV absorber (5) is a polymer compound having in its molecule a skeleton having the function of an UV absorber. For example, acrylic monomers and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, styrene, acetic acid) having a skeleton (benzophenone, benzotriazole, triazine) acting as an ultraviolet absorber in the side chain Examples thereof include those copolymerized with vinyl or the like. While conventional ultraviolet absorbers are generally low molecular weight molecules having a molecular weight of 200 to 400, the weight average molecular weight of the polymer ultraviolet absorber particles usually exceeds 10,000. Disadvantages of conventional low molecular weight ultraviolet absorbers such as compatibility with plastics and heat resistance are improved, and weather resistance can be imparted over a long period of time. Examples of the use form include a powder or a dispersion system dispersed in an organic solvent such as ethyl acetate, and an emulsion system dispersed in water.

  Specific examples of the polymeric ultraviolet absorber include coating polymeric ultraviolet absorbers ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG manufactured by Yushi Kogyo Co., Ltd. ULS-1383MG, ULS-1385MG, ULS-635MH, ULS-933LP, ULS-935LH, ULS-1935LH, HC-935UE, XL-504, XL-524, XL-547, XL-729, XL-730, etc. Can be mentioned. Preferably, the solubilizing solvent is water, alcohol or cellosolves. More preferably, the solubilizing solvent is water.

(6) Curing catalyst The curing catalyst (6) is a catalyst for hydrolysis and condensation (curing) of the silane compounds (1) to (4). Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, Examples thereof include inorganic acids such as perchloric acid and sulfamic acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, and p-toluenesulfonic acid.
Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

Among these curing catalysts (6), an organic acid can be preferably used because it can be highly dispersed even when the blending amount of the polymeric ultraviolet absorber (5) is increased and the transparency of the resulting film can be improved. In particular, organic carboxylic acids, especially acetic acid can be preferably used.
In addition, a curing catalyst may be used independently and may be used in combination of multiple.

(7) Solvent The coating composition of this invention is used in the state mixed with water and / or the organic solvent. The solvent (7) used in the present invention is not particularly limited as long as it can uniformly mix and disperse the above-mentioned components. For example, in addition to water, alcohols, aromatic hydrocarbons, ethers, ketones, Mention may be made of organic solvents such as esters. Among these organic solvents, specific examples of alcohol include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, and n-octyl. Alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene monomethyl ether acetate, diacetone alcohol , Methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and the like.
Specific examples of other solvents include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like. Is mentioned.
These may be used singly or in combination of two or more.

Although the compounding quantity of each component (1)-(7) can be set suitably, it is as follows, for example.
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound: preferably 10 to 80% by weight (more preferably 15 to 75% by weight)
(2) Aminosilane compound: 1 to 60% by weight (more preferably 3 to 40% by weight)
(3) Epoxysilane compound: 1 to 60% by weight (more preferably 5 to 50% by weight)
(4) Blocked isocyanate silane compound: 1 to 60% by weight (more preferably 5 to 60% by weight)
(5) Polymer ultraviolet absorber: 0.1 to 50% by weight (more preferably 5 to 50% by weight)
(6) Curing catalyst: 0.1 to 40% by weight (more preferably 0.1 to 30% by weight)
(7) Solvent: 5 to 1000 parts by weight (more preferably 20 to 800 parts by weight) when the total of components (1) to (6) is 100 parts by weight.

If the organoalkoxysilane compound or polyorganoalkoxysilane compound (1) is mixed in an amount exceeding 80% by weight, the adhesion may be lowered. If it is less than 10% by weight, the scratch resistance and film-forming property may be reduced. May decrease (crack, etc.).

  When the aminosilane compound (2) is mixed in an amount exceeding 60% by weight, the film-forming property is deteriorated (cracked), and when it is less than 1% by weight, the adhesion and scratch resistance may be significantly reduced. Furthermore, about the minimum of compounding quantity, as shown in an Example, using 3 weight% or more is preferable for abrasion-resistant expression.

  When the epoxysilane compound (3) exceeds 60% by weight, the transparency, adhesion, scratch resistance, and coating solution stability of the film are deteriorated. May decrease (crack). Furthermore, about a minimum of compounding quantity, as shown in an Example, it is preferable for film forming property expression to use 5 weight% or more. More preferably, it is 10% by weight or more.

When the blocked isocyanate silane compound (4) is mixed in an amount exceeding 60% by weight, the film forming property is lowered, and when it is less than 1% by weight, the coating liquid stability may be lowered. Furthermore, as for the lower limit of the blending amount, as shown in the examples, it is preferable to use 5% by weight or more for the expression of durability (moisture resistance). More preferably, it is 10% by weight or more.
The blending amount of the blocked isocyanate silane compound (4) is the total amount of the isocyanate silane compound and the blocking agent.
The compounding molar ratio of the isocyanate silane compound and the blocking agent is usually 0.9 to 1.1: 0.9 to 1.1, preferably 0.95 to 1.05: 0.95 to 1.05. It is.

  When the polymer ultraviolet absorber (5) is mixed in an amount exceeding 50% by weight, the scratch resistance is remarkably lowered, and when it is less than 0.1% by weight, sufficient weather resistance may not be exhibited.

  If the curing catalyst (6) exceeds 40% by weight, the stability of the coating solution may be reduced, and if it is less than 0.1% by weight, it may cause poor curing.

  The amount of the solvent (7) is preferably 5 to 1000 parts by weight, more preferably 20 to 800 parts by weight, and particularly preferably 50 to 600 parts when the total of the components (1) to (6) is 100 parts by weight. Used in the range of parts by weight.

In addition, the coating composition of the present invention can also contain a leveling agent and a lubricant for the cured film. Examples of such additives include a copolymer of polyoxyalkylene and polydimethylsiloxane, and polyoxyalkylene. A copolymer of fluorocarbon and the like can be used.
In addition, a light stabilizer, a weather resistance imparting agent, a colorant, or an antistatic agent can be added as necessary.

The coating composition is prepared by mixing the components (1) to (7).
Preferably, a first mixed solution containing at least component (1) and component (4) is prepared, and finally component (2) is mixed.
Thus, when prepared separately, the liquid storage stability of the coating composition (such as non-gelling) is improved, which is preferable.
For example, after mixing components (1), (3), (5) to (7), component (4) is added, and finally component (2) is mixed.
Component (7) can be added to the coating composition to further dilute the coating composition after preparation.

The coating composition of the present invention can be made into a cured film (cured film) by curing by a conventional method. Specifically, the coating composition is sprayed, dipped, curtain flow, bar coater, roll coating, etc. on the substrate of a resin molded product (injection molded product, film, sheet, etc.) that is the target for forming a cured film. Is applied by a known method to form a coating film. The thickness of the coating film is adjusted so that the thickness of the cured film is preferably 1 to 50 μm, more preferably 2 to 20 μm.
Then, a cured film is obtained by heating and curing at appropriate curing conditions, usually 80 to 190 ° C., preferably 100 to 140 ° C., for 10 minutes to 24 hours, preferably 30 minutes to 3 hours.

In the cured film obtained from the coating composition of the present invention, organic fine particles (component (5)) are dispersed in the film. The cured film of the present invention preferably has a visible light transmittance of 80% or more, more preferably 85% or more. Moreover, Preferably a haze value is 10% or less, More preferably, it is 5% or less. Such a cured film is excellent in ultraviolet resistance and is a highly transparent cured film.
The matrix having Si—O bonds in which the organic fine particles (component (5)) are dispersed is derived from the components (1), (2), (3) and (4).

  A laminate including a substrate and a cured film obtained from the coating composition of the present invention has excellent scratch resistance, weather resistance, and boiling resistance.

In the examples and comparative examples, the following components were used.
Ingredient (1):
MTMS-A (Trifunctional polyalkoxysilane compound)
(Made by Tama Chemical Industry Co., Ltd.)

Ingredient (5):
ULS-383MG (Ultraviolet absorbing skeletal species: benzophenone)
ULS-1383MG (Ultraviolet absorbing skeletal species: benzotriazole)
ULS-1385MG (Ultraviolet absorbing skeletal species: benzotriazole)
All manufactured by Otsuka Oil Industry Co., Ltd. (water dispersion / solid content concentration 30%)

Polycarbonate substrate:
Idemitsu Kosan Co., Ltd. IV2200R (weatherproof grade), 3 mm thick (visible light transmittance 90%, haze value 1%)

Example 1
Prepared according to the ingredients and preparations in Table 1.
A sample tube with a capacity of 50 g was charged with ULS-1385MG (component (5)), 1-methoxy-2-propanol (component (7)), ion-exchanged water (component (7)), and stirred at 700 rpm while acetic acid was added. (Component (6)), methyltrimethoxysilane (component (1)), dimethoxy-3-glycidoxypropylmethylsilane (component (3)), 20% p-toluenesulfonic acid methanol solution (component (6)) In the order of 1 minute. Subsequently, after stirring at room temperature for 60 minutes, the mixture was allowed to stand for 1 day, which was designated as solution A.
A sample tube with a capacity of 20 g was charged with 3-isocyanatopropyltriethoxysilane and 2-butanone oxime (isocyanate group blocking agent), stirred at 500 rpm for 10 minutes, and allowed to stand for 1 day. . The blocking of the isocyanate group was confirmed by disappearance of the peak of the isocyanate group by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of blocked isocyanate silane compound (4).

A 200 ml three-necked flask equipped with a condenser tube was charged with solution A and a stirring bar, and heated at 80 ° C. for 3 hours at 600 rpm under a nitrogen stream. Then, B liquid was added and it heated at 80 degreeC on the same conditions for 4 hours.
Further, 3-aminopropyltrimethoxysilane (component (2)) was added dropwise thereto over 2 minutes, and then heated at 80 ° C. for 6 hours. Subsequently, the coating composition was obtained by allowing to stand for 1 week at 25 ° C. in a dark place. The liquid stability was evaluated about the obtained coating composition. The evaluation results are shown in Table 1.

  The coating composition obtained above was applied to the surface of a polycarbonate resin having a thickness of 3 mm with a bar coater so that the cured film had a thickness of 7 μm, and cured in an oven under a nitrogen stream at 130 ° C. for 2 hours. A transparent laminate having a cured coating on the surface was obtained. The physical properties of the obtained laminate were evaluated. The evaluation results are shown in Table 1.

The evaluation method of the obtained coating composition and laminated body is as follows.
(1) Liquid stability The container was stored sealed at room temperature for 14 days, and the presence or absence of gelation was determined visually. About the thing which is not gelatinized, the viscosity was measured by A & D tuning fork type vibration viscometer SV-10, and the thing whose change rate from the initial stage was less than 3 times was made favorable.

(2) Film appearance The appearance of the cured film (presence or absence of foreign matter or mottled pattern) and the presence or absence of cracks were visually confirmed.

(3) Visible light transmittance and haze It measured in the state of a laminated body with a polycarbonate substrate in the direct reading haze computer (Suga Test Instruments Co., Ltd. make, HGM-2DP).

(4) Equivalent weight of SiO ₂ derived from Si compound in cured film The ratio of oxide was determined by thermogravimetry (nitrogen) on a sample obtained by thermosetting the coating liquid on a Teflon (registered trademark) petri dish. The temperature was raised at 20 ° C./min, room temperature to 800 ° C., and the amount of the residue at 800 ° C. of the sample was obtained.

(5) Volume fraction of organic fine particles in cured film The volume fraction of organic fine particles is obtained by observing a cross section of a thermosetting film on a resin substrate with a TEM (transmission electron microscope) and presenting in particles of 1.5 μm. Is obtained by dividing the area by the value of “thickness of observation sample ÷ average particle diameter of organic fine particles” using free software manufactured by NIH, USA.

(6) Abrasion resistance Using a wear wheel CS-10F and a Taber abrasion tester (rotary abrasion tester) (Toyo Seiki Co., Ltd., No. 430), a 100-turn Taber abrasion test was conducted at a load of 500 g, and a Taber abrasion test was conducted. The difference between the haze after the haze and the Taber abrasion test (ΔH) is less than 10 and the difference between Δ and 10 is less than 15 and Δ is 15 or more (haze = Td / Tt × 100, Td: Scattered light transmittance, Tt: total light transmittance).
The difference in haze between the polycarbonate resin substrates used in the examples and comparative examples was ΔH = 30.

(7) Adhesion In accordance with JIS K5400, a sample was cut into 11 grids at 2 mm intervals with a razor blade to make 100 grids, and a commercially available cellophane tape (“CT-24 (width 24 mm)”). , Manufactured by Nichiban Co., Ltd.) with the abdomen of the finger well, and then peeled off rapidly at an angle of 90 °, and the remaining number (X) of the film without peeling was displayed as X / 100. .

(8) Boiling resistance A sample in which a cured film is formed on a polycarbonate resin is immersed in boiling water in a stainless steel beaker for a predetermined time. Changes in appearance, adhesion, and film thickness were evaluated. The film thickness was measured with an optical film thickness meter FE-3000 manufactured by Otsuka Electronics. A film thickness reduction rate of less than 10% was evaluated as .largecircle., 10% to less than 15% as .DELTA., And 15% or more as x.

(9) Weather resistance A xenon weather test (Atlas Ci165, output 6.5 kW, black panel temperature 63 ° C., humidity 50%) was performed. The weather resistance was evaluated by the change in adhesion before and after the test.

(10) Cold and thermal shock resistance A thermal shock test (ESCEC cold thermal shock device, TSA-200D-W, -30 ° C for 1 hour, 80 ° C for 1 hour for 100 cycles) was performed. The heat resistance test was evaluated by the change in adhesion between before and after the test.

(11) Heat resistance A heat resistance tester (manufactured by Tabai, PS-222) was used under the conditions of 80 ° C. and 720 hours. The heat resistance was evaluated by the change in adhesion before and after the test.

(12) Average particle diameter of organic fine particles in cured film Cross-sectional observation of the thermosetting film was performed with a TEM (transmission electron microscope), and 10 particles existing in the 1 μm square were selected, and NIH (National Institute of Health, USA) was selected. ) Free software: NIH Image 1.63 was used to determine the average particle size.
There are ◯ having an average particle size of 200 nm or less, x having an average particle size of greater than 200 nm, and those having a particle size of 200 nm or less, but the particles were fused to form an amoeba shape having a particle size of greater than 200 nm. The thing with what exists was set as △.
In addition, the average particle diameter in Example 1-8 was 40-60 nm, and had formed the dispersed structure.

Comparative Example 1
After adding 3-aminopropyltrimethoxysilane (component (2)) dropwise and heating at 80 ° C. for 30 minutes, it was prepared according to the components and preparation amounts shown in Table 2 in the same manner as in Example 1, and the obtained composition The laminate was evaluated. The evaluation results are shown in Table 2.

Examples 2 and 3
The heat treatment conditions after adding the B liquid to the A liquid were set at 65 ° C. for 4 hours, and 3-aminopropyltrimethoxysilane (component (2)) was added to the mixed heat treatment liquid of the A liquid and the B liquid. Except that the heat treatment conditions were set at 65 ° C. for 6 hours, in the same manner as in Example 1, the ingredients and preparation amounts shown in Table 1 were prepared, and the obtained compositions and laminates were evaluated. The evaluation results are shown in Table 1.

Examples 4-8, Comparative Examples 2-4
In the same manner as in Example 1, preparation was performed according to the components and preparation amounts shown in Table 1 or Table 2, and the obtained composition and laminate were evaluated. The evaluation results are shown in Table 1 or Table 2.
The volume fraction of organic fine particles in the cured coating produced in Example 6 was 23% by volume.

  The present invention includes automobile interior parts such as meter covers, windshields for motorcycles and tricycles, resin automobile windows (various vehicle windows), plastic building material windows, roofs for construction machinery, road light transmission boards (sound insulation boards), and corrections. In addition to eyeglass lenses such as sunglasses, sports, safety glasses, etc., optical discs, displays, mobile phone parts, lighting parts such as street lights, windshields, various resin materials for protective shields, especially polycarbonate materials Development is possible, and it can be suitably used as a glass substitute member.

Claims (19)

A coating composition comprising the following components (1) to (7).
Organoalkoxysilane compound represented by (1) the following equation (1), or the poly organoalkoxysilane compound organoalkoxysilane compound is a partial condensate bound by siloxane bonds _{^{(R 1) m Si (OR}} 2) 4 _-M (1)
(In the formula, R ¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ² is an alkyl group having 1 to 4 carbon atoms or an ether group, and m is an integer of 1 or 2.)
(2) A compound represented by the following formula (2), N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminosilane compound selected from (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane (R ¹¹ ) _n Si (OR ² ) _{4− n} (2)
(In the formula, R ¹¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group, aminoalkyl group represented by NH ₂ — (CH ₂ ) _x —. , R 1 -NH- represents an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups, and at least one of R ¹¹ is an amino group, an aminoalkyl group , An alkyl group having 1 to 3 carbon atoms substituted with any of the alkylamino groups, x in the aminoalkyl group is an integer of 1 to 3, and R in the alkylamino group has 1 to 3 carbon atoms. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(4) Blocked isocyanate silane compound (5) Polymer ultraviolet absorber (6) Curing catalyst (7) Solvent R ^{1 in} formula (1) may be the same or different and is an alkyl group having 1 to 10 carbon atoms,
The aminosilane compound (2) is a compound represented by the formula (2), and R ^{11 in} the formula (2) may be the same or different; an alkyl group having 1 to 4 carbon atoms; or an amino group, NH ₂ — (CH ₂₎ x _- aminoalkyl group represented by a one or more alkyl groups having 1 to 3 carbon atoms which is substituted with a group selected from the group consisting of alkyl amino group represented by R-NH-, R ¹¹ At least one of these is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, and an alkylamino group,
R ^{21 in} formula (3) may be the same or different, and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms; or a glycidoxy group and a 3,4-epoxycyclohexyl group The coating composition according to claim 1, which is an alkyl group having 1 to 3 carbon atoms, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. object.   The aminosilane compound (2) is N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl). -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxy The coating composition according to claim 1, which is silane or N-methylaminopropyltriethoxysilane. The coating composition according to any one of claims 1 to 3, wherein a blending amount of the components (1) to (7) is in the following range.
(1) Organoalkoxysilane compound or polyorganoalkoxysilane compound:
10-80% by weight
(2) Aminosilane compound: 1 to 60% by weight
(3) Epoxysilane compound: 1 to 60% by weight
(4) Blocked isocyanate silane compound: 1 to 60% by weight
(5) Polymer ultraviolet absorber: 0.1 to 50% by weight
(6) Curing catalyst: 0.1 to 40% by weight
(7) Solvent: 5 to 1000 parts by weight when the total of components (1) to (6) is 100 parts by weight   The coating composition according to any one of claims 1 to 4, wherein the blocked isocyanate silane compound is a blocked isocyanate silane compound blocked with an oxime compound.   The coating composition according to claim 1, wherein the curing catalyst is an organic acid.   The coating composition according to claim 1, wherein the curing catalyst is acetic acid.   The polymer ultraviolet absorbent particles are obtained by copolymerizing an acrylic monomer having a benzophenone-based, benzotriazole-based, or triazine-based skeleton in a side chain with another ethylenically unsaturated compound. The coating composition according to any one of the above.   The coating composition according to any one of claims 1 to 8, wherein the polymer ultraviolet absorber particles have a weight average molecular weight exceeding 10,000.   The coating composition according to any one of claims 1 to 9, wherein the polymeric ultraviolet absorber is an organic fine particle having an average particle diameter of 1 to 200 nm.   The cured film formed by hardening | curing the coating composition in any one of Claims 1-10.   The cured film according to claim 11, wherein a volume fraction in the cured film of the organic fine particles is 0.5 to 70% by volume. The curing in terms of SiO ₂ by weight of Si derived component contained in the film, the cured film according to claim 11 or 12 30 to 80 wt% of the total weight of the cured film.   The resin laminated body formed by forming the cured film in any one of Claims 11-13 on a resin base material. The manufacturing method of the coating composition prepared by mixing the following component (1)-(7).
Organoalkoxysilane compound represented by (1) the following equation (1), or the poly organoalkoxysilane compound organoalkoxysilane compound is a partial condensate bound by siloxane bonds _{^{(R 1) m Si (OR}} 2) 4 _-M (1)
(In the formula, R ¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ² is an alkyl group having 1 to 4 carbon atoms or an ether group, and m is an integer of 1 or 2.)
(2) A compound represented by the following formula (2), N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminosilane compound selected from (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane (R ¹¹ ) _n Si (OR ² ) _{4− n} (2)
(In the formula, R ¹¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group, aminoalkyl group represented by NH ₂ — (CH ₂ ) _x —. , R 1 -NH- represents an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups, and at least one of R ¹¹ is an amino group, an aminoalkyl group , An alkyl group having 1 to 3 carbon atoms substituted with any of the alkylamino groups, x in the aminoalkyl group is an integer of 1 to 3, and R in the alkylamino group has 1 to 3 carbon atoms. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; vinyl group; phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(4) Blocked isocyanate silane compound (5) Polymer ultraviolet absorber (6) Curing catalyst (7) Solvent R ^{1 in} formula (1) may be the same or different and is an alkyl group having 1 to 10 carbon atoms,
The aminosilane compound (2) is a compound represented by the formula (2), and R ^{11 in} the formula (2) may be the same or different; an alkyl group having 1 to 4 carbon atoms; or an amino group, NH ₂ — (CH ₂₎ x _- aminoalkyl group represented by a one or more alkyl groups having 1 to 3 carbon atoms which is substituted with a group selected from the group consisting of alkyl amino group represented by R-NH-, R ¹¹ At least one of these is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, and an alkylamino group,
R ^{21 in} formula (3) may be the same or different, and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms; or a glycidoxy group and a 3,4-epoxycyclohexyl group The coating composition according to claim 15, which is an alkyl group having 1 to 3 carbon atoms, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. Manufacturing method.   The aminosilane compound (2) is N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl). -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxy The method for producing a coating composition according to claim 15, which is silane or N-methylaminopropyltriethoxysilane. Producing a first mixed liquid containing at least component (1) and component (4);
The method for producing a coating composition according to any one of claims 15 to 17, wherein component (2) is finally mixed.   The manufacturing method of the cured film including the process of heating and hardening the coating composition in any one of Claims 1-10.