JP2011231169A - Acrylic resin film having laminated curable coated film and molded product obtained by laminating the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin film having a laminated curable coated film superior in abrasion resistance, crack resistance, and moldability and a molded product obtained by laminating the film on a base material.SOLUTION: The acrylic resin film has a laminated curable coated film which is composed of a curable composition including a siloxane compound (A) obtained by hydrolysis condensation of at least one of an alkyl silicate and an organosilane and has a ratio of a peak area derived from a siloxane bond in the infrared absorption spectrum to a peak area derived from Si-CHof 16-21.

Description

  The present invention relates to an acrylic resin film on which a curable coating film excellent in wear resistance, crack resistance and workability is laminated, and a molded body obtained by laminating the film on a substrate.

  In recent years, transparent plastic materials such as acrylic resin and polycarbonate resin, which are excellent in crush resistance and light weight, have been widely used as an alternative to transparent glass. However, transparent plastic materials have poor wear resistance and weather resistance compared to glass, and yellowing and whitening occur over time. In order to improve these disadvantages, a method of forming a transparent plastic molded body having a curvature and then applying a coating composition of an ultraviolet curable acrylic resin or silicone resin to the molded body has been performed. There is a problem that the work is complicated.

  Therefore, a technique for decorating a three-dimensional molded body with a thermoplastic protective film in which an ultraviolet curable acrylic resin composition mainly composed of urethane acrylate is laminated has been proposed (Patent Document 1). However, the acrylic resin composition has good followability to the molded product, but has insufficient wear resistance.

  Also, after applying and curing an acrylic resin primer on the polycarbonate film or sheet surface, the organopolysiloxane composition is applied, and the multilayer film or sheet is mounted in an injection mold without being completely cured. Then, a technique has been proposed in which molten polycarbonate is injected into a mold and post-cured after mold release (Patent Document 2). However, this method has a drawback in that since the base material is polycarbonate, a primer layer containing an ultraviolet absorber or HALS for protecting the base material from ultraviolet rays is required.

JP 2002-240202 A JP 09-24553 A

  An object of the present invention is that an acrylic resin film in which a primer layer is not required even when applied to a polycarbonate substrate, and a curable coating film excellent in appearance, wear resistance, crack resistance, and workability is laminated. Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that the combination of a siloxane compound having a specific structure and an acrylic resin film having a specific composition has excellent appearance, wear resistance and crack resistance. I found. In addition, it was found that if the peak area derived from the siloxane bond in the infrared absorption spectrum / the peak area derived from Si—CH ₃ is in a specific range, a laminate having excellent workability can be formed. It came to complete.

That is, the gist of the present invention is as follows.
Alkyl silicates represented by general formula (1)

（式中Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は独立して炭素数１〜５のアルキル基または、炭素数１〜４のアシル基を示し、ｎは３〜２０のいずれかの整数を示す。）
及び一般式（２）で示されるオルガノシラン類

(In the formula, R ¹ , R ² , R ³ and R ⁴ independently represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 20) Show.)
And organosilanes represented by the general formula (2)

（式中Ｒ^５は炭素数１〜１０のアルキル基、ハロゲン化アルキル基、アリール基、エポキシ基、(メタ)アクリロイル基、メルカプト基、アミノ基、またはイソシアネート基を含有する有機基を示し、Ｒ^６は炭素数１〜５のアルキル基、または、炭素数１〜４のアシル基を示し、ａは１〜３の整数を示す。）の少なくとも一方を加水分解縮合して得られたシロキサン化合物（Ａ）を含む硬化性組成物からなり、且つ、その赤外線吸収スペクトルのシロキサン結合に由来するピーク面積／Ｓｉ−ＣＨ_３に由来するピーク面積の比が１６〜２１である硬化性塗膜が積層されたアクリル樹脂フィルム（Ｂ）にある。

(Wherein R ⁵ represents an organic group containing an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aryl group, an epoxy group, a (meth) acryloyl group, a mercapto group, an amino group, or an isocyanate group; R ⁶ represents an alkyl group having 1 to 5 carbon atoms, or an acyl group having 1 to 4 carbon atoms, and a represents an integer of 1 to 3). A curable coating film comprising a curable composition containing A) and having a ratio of the peak area derived from the siloxane bond in the infrared absorption spectrum / the peak area derived from Si—CH ₃ is 16 to 21 is laminated. Acrylic resin film (B).

  The gist of the present invention resides in a molded body in which the aforementioned acrylic resin film is laminated on the base material (C).

  According to the present invention, it is possible to provide an acrylic resin film in which an excellent appearance, wear resistance, crack resistance, and workability are excellent and an acrylic resin film in which the film is laminated, and a molded body in which the film is laminated.

It is an example of the infrared absorption spectrum in the coating film of this invention.

<Siloxane compound (A)>
The siloxane compound (A) constituting the present invention is a hydrolysis obtained by hydrolysis / condensation of at least one of the alkyl silicates represented by the general formula (1) and the organosilanes represented by the general formula (2). -Condensate. Such a siloxane compound is a high molecular weight oligomer in which a cross-linked structure is formed between molecules by previously hydrolyzing and condensing at least one of alkyl silicates and organosilanes, thereby improving curability in the composition. And the physical property of the hardened | cured material suitable for the protective film obtained can be improved. In addition, since the siloxane compound is an oligomer having a high molecular weight, the shrinkage caused by polycondensation during curing and the accompanying stress can be reduced, resulting in the reduction of cracks and the improvement of film adhesion to the substrate. Can do.

In the alkyl silicate represented by the general formula (1) that forms the siloxane compound (A), in the formula (1), R ¹ , R ² , R ³ , and R ^{4 4} are independently 1 to 5 carbon atoms. An alkyl group or an acyl group having 1 to 4 carbon atoms. These groups may be the same as or different from each other. n represents the number of repeating units of the alkyl silicate, and is an integer of 3 to 20. When n is 3 or more, the molecular weight of the siloxane compound obtained by hydrolysis / condensation of alkyl silicates is large, and it is possible to suppress deterioration in curability and film formability of the resulting curable composition. Moreover, if n is 20 or less, gelation can be suppressed during hydrolysis and condensation. N is preferably an integer of 4 to 10 (concentration equivalent to silica: equivalent to about 51 to 54% by mass) from the viewpoint that good curability and film physical properties can be obtained and gelation can be suppressed. Here, the silica equivalent concentration means the ratio between the mass of the alkyl silicate and the mass of SiO ₂ obtained when the alkyl silicate is completely hydrolyzed and condensed.

Specific examples of the alkyl silicates represented by the general formula (1) include methyl silicates in which R ^{1 to} R ⁴ are methyl groups, ethyl silicates in which R ^{1 to} R ⁴ are ethyl groups, and R ^{1 to} R ⁴ are isopropyl silicate is an isopropyl ^group, R 1 to R ⁴ is a n- propyl group n- propyl ^silicate, R 1 to R ⁴ is a n- butyl group n- butyl ^silicate, R 1 to R ⁴ is n- pentyl Examples thereof include n-pentyl silicate which is a group, acetyl silicate in which R ^{1 to} R ⁴ are acetyl groups, and the like. Of these, methyl silicate and ethyl silicate are preferred because they are easily available and have a high hydrolysis rate.

As organosilanes represented by the general formula (2) for forming the siloxane compound (A), in the formula (2), R ⁵ is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aryl group, an epoxy. An organic group containing a group, a (meth) acryloyl group, a mercapto group, an amino group, or an isocyanate group, R ⁶ represents an alkyl group having 1 to 5 carbon atoms, or an acyl group having 1 to 4 carbon atoms, a represents an integer of 1 to 3. In the formula, when a plurality of R ⁵ and R ⁶ are present, they may be the same as or different from each other. R ⁶ is preferably a methyl group or an ethyl group from the viewpoint of easy production and a high hydrolysis rate.

  Specific examples of organosilanes represented by the general formula (2) include methyltriethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltriethoxysilane P-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- List mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, etc. Can do. Among these, methyltriethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and dimethyldimethoxysilane can be mentioned as preferable examples. In the present invention, these can be used as one kind or a mixture of two or more kinds.

  Hydrolysis of the alkyl silicates represented by the general formula (1) and the organosilanes represented by the general formula (2) may be carried out by any method, for example, the alkyl silicates and the above-mentioned At least one of the organosilanes is mixed with an alcohol, and water is added, for example, about 0.25 to 250 moles per mole of alkoxyl group, and an acid such as hydrochloric acid or acetic acid is added thereto to make the solution acidic ( For example, the pH can be adjusted to 2 to 5) and stirred.

  In addition, the hydrolysis is performed by mixing at least one of the above alkyl silicates and the above organosilanes with alcohols, and adding water, for example, about 0.25 to 250 moles with respect to 1 mole of the alkoxyl group, for example, 30 to 100. It can be based on a method of heating to ° C. The alcohol generated during the hydrolysis may be distilled out of the system. Condensation subsequent to hydrolysis can be allowed to proceed by leaving the alkyl silicates and organosilanes in a hydrolyzed state. At that time, the progress of the condensation can be accelerated by controlling the pH to be near neutral (for example, pH 6 to 7). The water generated during the condensation may be distilled out of the system.

  The mixing ratio when the alkylsilicate represented by the general formula (1) and the organosilane represented by the general formula (2) in the hydrolysis / condensation are used in combination is 1 mol of the organosilane. Alkyl silicates are preferably 0.01 to 1.0 mol, more preferably 0.01 to 0.1 mol.

  Examples of the initiator for curing the siloxane compound (A) include a thermosetting system and a photocuring system. Examples of the thermosetting initiator include alkali metal salts and ammonium salts of carboxylic acids, perchlorates, metal complex salts of acetylacetone, quaternary ammonium and quaternary ammonium salts.

  Examples of the photocuring initiator include diphenyliodonium compounds, triphenylsulfonium compounds, aromatic sulfonium compounds, diazodisulfone compounds, and the like. Specific examples include Irgacure 250 (product name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Adekaoptomer SP-150 and SP-170 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Syracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990 and Cyracure UVI-6950 (manufactured by Union Carbide, USA), DAICATII (manufactured by Daicel Chemical Industries, Ltd., product name), UVAC1591 (Daicel Cytec Corporation) ), Product name), CI-2734, CI-2855, CI-2823 and CI-2758 (manufactured by Nippon Soda Co., Ltd., product name), Syracure UVI-6992 (manufactured by Dow Chemical Japan Co., Ltd., product name) , Sun-Aid SI-L85, SI-L110, SI-L1 5, SI-L150, SI-L160, SI-H15, SI-H20, SI-H25, SI-H40, SI-H50, SI-60L, SI-80L and SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) , Product name), CPI-100P and CPI-101A (manufactured by San Apro Co., Ltd., product name). As the initiator, a thermosetting system and a photocuring system can be used alone or in combination of two or more. Moreover, it can also be used combining heat and light.

  Although the compounding quantity of the said initiator is not specifically limited, The inside of the range of 0.01-10 mass parts is preferable with respect to 100 mass parts of sclerosing | hardenable component total amount.

  If it is 0.01 mass part or more, it will fully harden | cure by irradiation of an active energy ray, and it exists in the tendency for the hardened | cured material suitable for a favorable protective film to be obtained. Moreover, if it is 10 mass parts or less, about hardened | cured material, a crack does not generate | occur | produce, coloration is suppressed, and it exists in the tendency for surface hardness and abrasion resistance to become favorable.

  The curable composition containing the siloxane compound (A) of the present invention contains the siloxane compound (A), an initiator, and a solvent. In addition, if necessary, inorganic fine particles, polymers, polymer fine particles, fillers, dyes , Pigments, pigment dispersants, flow regulators, leveling agents, antifoaming agents, ultraviolet absorbers, light stabilizers, antioxidants, gel particles, fine particle powders, and the like.

  In order to form a coating film of the curable composition, a roll coating method, a gravure coating method, a flexo coating method, a screen, a flow coating method, a dipping method, or the like can be used.

<Infrared absorption spectrum>
In the present invention, the curable coating film of the curable composition containing the siloxane compound (A) is measured by an FT-IR total reflection method (ATR; Attenuated Total Reflectance). FIG. 1 is an example of an infrared absorption spectrum of a siloxane oligomer measured by this method.

Siloxane bond has a absorption in 960～1240Cm ^-1, 1, and the line segment cd a line segment connecting the point d that indicates the absorbance at c and 960 cm ^-1 that indicates the absorbance at 1240 cm ^-1 , The area enclosed is the peak area derived from the siloxane area.

Further, Si-CH ₃ bonds have a absorption in 1250～1300Cm ^-1, 1, a line segment connecting the a point indicating the absorbance at b and 1300 cm ^-1 that indicates the absorbance at 1250 cm ^-1 Is the line segment ab, and the enclosed area is the peak area derived from the Si—CH ₃ bond.

In the present invention, the ratio of 960 to 1240 cm ⁻¹ (Si—O—Si stretching vibration) peak area / 1250 to 1300 cm ⁻¹ (Si—CH ₃ stretching vibration) peak area is set to 16 to 21.

As the measurement conditions, a Ge crystal may be used with an incident angle of 45 ° and a single reflection measurement. For example, an FT-IR (trade name: “NEXUS470”, manufactured by Thermo Nicolet Co., Ltd.) and an ATR measurement accessory (product) The name “FOUNDATION ThunderDome” (Spectratech) is attached, and the measurement is performed with a resolution of 4 cm ⁻¹ and 32 integrations. The peak area can be obtained by an arbitrary method, for example, using an integration tool of FT-IR analysis software (trade name “OMNIC”, manufactured by Thermo Nicolay Co., Ltd.).

  If the FT-IR area ratio is 16 or more, there is no stickiness of the film and the film is easy to handle, and if it is 21 or less, the flexibility of the film increases and the processability of the three-dimensional object becomes good.

The method for setting the coating film to 960 to 1240 cm ⁻¹ (Si—O—Si stretching vibration) peak area / 1250 to 1300 cm ⁻¹ (Si—CH ₃ stretching vibration) peak area = 16 to 21 is particularly limited. However, it is achieved, for example, by leaving the coating film at a temperature of 30 to 100 ° C. for 5 to 30 minutes to form a curable coating film.

  Examples of the curing of the coating film include vacuum ultraviolet rays, ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, γ rays, heat, and the like. One of these may be used alone, or a plurality of different ones may be used. When different types are used, they can be irradiated simultaneously or sequentially.

  When making the curable composition of this invention into a cured film, 0.5-100 micrometers etc. can be mentioned as thickness of a film, for example.

<Acrylic resin film (B)>
The acrylic resin film (B) constituting the present invention is not particularly limited. Among them, a film comprising 100 parts by mass in total of 1 to 100 parts by mass of the rubber-containing multistage polymer (x) and 99 to 0 parts by mass of the acrylic (co) polymer (y) is more preferable.

<Rubber-containing multistage polymer (x)>
The rubber-containing multistage polymer (x) used in the present invention is obtained by polymerizing a monomer or a monomer mixture in the presence of rubber.

  The rubber in the present invention is a polymer having a glass transition temperature of 10 ° C. or lower, which contains a crosslinkable monomer component as a constituent component. Although the kind is not specifically limited, For example, the rubber | gum comprised from what polymerized the alkyl acrylate-type monomer is mentioned.

  As the rubber used in the present invention, one obtained by one or more stages of polymerization can be used. Further, the rubber may be polymerized at any stage. For example, a rubber obtained by polymerizing monomers constituting the rubber in the presence of a polymer having a glass transition point of room temperature or higher can also be used.

  Hereinafter, preferred examples of the rubber-containing multistage polymer (x) described above will be specifically described.

  For the production of rubber, known alkyl acrylates having 1 to 8 carbon atoms in the alkyl group are used, among which butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable.

  Moreover, it is preferable that the usage-amount is the range of 5-100 mass% in all the rubber | gum. When the content is 5% by mass or more, the elongation of the resulting acrylic resin film is improved, and the film may be easily formed or processed. A more preferable use range is 10 to 90% by mass.

  In the rubber, other vinyl monomers copolymerizable with the above alkyl acrylate may be used in an amount of 95% by mass or less. Specific examples of such other vinyl monomers include methyl methacrylate and butyl. Preferred are alkyl methacrylates such as methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile, and the like, and one or more of these can be used.

  The crosslinkable monomer used in the rubber is not particularly limited, but preferably ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, and the like. Alkylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allylcinnamate, etc. More than seeds can be used.

  The crosslinkable monomer is preferably used in the range of 0.1 to 10% by mass in the total rubber. When the content is 0.1% by mass or more, the amount of monomer grafted on the rubber layer increases. Although it may be used in excess of 10% by mass, an effect commensurate with the added amount is not exhibited. A more preferable use range is 0.3 to 7% by mass.

  As a monomer to be polymerized in the presence of rubber, alkyl methacrylate is preferably used in an amount of 50% by mass or more. Specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate, and one or more of these can be used. Particularly preferred is methyl methacrylate.

  Furthermore, at least one of other vinyl monomers copolymerizable with these can be used in an amount of 50% by mass or less. Specific examples of such vinyl monomers include methyl acrylate, butyl acrylate, and cyclohexyl acrylate. Alkyl acrylates such as styrene, acrylonitrile and the like, and one or more of these can be used. Particularly preferred is methyl acrylate.

  The monomer or monomer mixture is preferably used in an amount of 10 to 400 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of rubber.

  The rubber-containing multistage polymer (x) can be obtained by ordinary emulsion polymerization. In addition, you may use a chain transfer agent, another polymerization adjuvant, etc. at the time of superposition | polymerization. Known chain transfer agents can be used, but mercaptans are preferred. The chain transfer agent is preferably used at a ratio of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total amount of the monomer or monomer mixture in order to control the gel content and the molecular weight of the polymer. .

  As the surfactant used in preparing the emulsion, anionic, cationic and nonionic surfactants can be used, and anionic surfactants are particularly preferable. Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, N-lauroyl sarcosine sodium, alkenyl succinate dipotassium salt, sulfate ester salt such as sodium lauryl sulfate, etc. , Sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate And phosphoric acid ester salts. Of these, phosphate esters such as sodium polyoxyethylene alkyl ether phosphates are preferred.

  The amount of the surfactant may be determined by the mass average particle diameter of the rubber-containing multistage polymer (x), the dispersion stability of the polymer latex, and the like. It is preferable to mix | blend in the ratio of 0.1-5.0 mass parts with respect to 100 mass parts of monomers or monomer mixture whole quantity.

  Preferable specific examples of the surfactant include NC-718 manufactured by Sanyo Kasei Kogyo Co., Ltd., Phosphanol RS-610NA, Phosphanol LS-529, Phosphanol RS-620NA, Phosphorol manufactured by Toho Chemical Industry Co., Ltd. Nord RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, Latemu P-0404, Latemulu P-0405, Latemulu P-0406, Latemulu P-0407 manufactured by Kao Corporation All of the above are trade names).

  Moreover, as a method for preparing an emulsion, a method in which a monomer component is charged in water and then a surfactant is added, a method in which a surfactant is charged in water and then a monomer component is charged, monomer Examples thereof include a method in which a surfactant is charged into a component and then water is added. Among these, the method of charging the surfactant after charging the monomer component into water and the method of charging the monomer component after charging the surfactant into water include the rubber-containing multistage polymer (x). As a method for obtaining

  Examples of the mixing device for preparing the emulsion include a stirrer equipped with a stirring blade; various forced emulsification devices such as a homogenizer and a homomixer; a membrane emulsification device and the like.

  Further, the emulsion to be prepared may have either a W / O type or an O / W type dispersion structure, particularly an O / W type in which oil droplets of monomer components are dispersed in water, Those having an oil droplet diameter of 100 μm or less are preferred.

  Examples of the polymerization initiator used when the monomer or monomer mixture is polymerized include a peroxide, an azo initiator, a redox initiator combined with an oxidizing agent / reducing agent, and the like. Among these, redox initiators are preferable, and sulfoxylate initiators in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are combined are particularly preferable. The addition amount of the polymerization initiator is appropriately determined according to the polymerization conditions and the like. Moreover, the addition method of a polymerization initiator may be either a method of adding to one or both of an aqueous phase and a monomer phase (oil phase).

  As a method for polymerizing the rubber-containing polymer (x), in particular, the temperature of the aqueous solution containing ferrous sulfate, disodium ethylenediaminetetraacetate and Rongalite charged in the reactor is raised to the polymerization temperature, and then the first stage. The monomer mixture and a polymerization initiator such as peroxide mixed with water and a surfactant are fed into the reactor for polymerization, and then the second stage monomer mixture A method in which a monomer component as a raw material is supplied to a reactor together with a polymerization initiator such as peroxide to polymerize is preferable.

  The polymerization temperature varies depending on the type or amount of the polymerization initiator, but is usually preferably 40 ° C. or higher, more preferably 60 ° C. or higher, preferably 120 ° C. or lower, more preferably 95 ° C. or lower.

  The polymer latex containing the rubber-containing polymer (x) obtained by the above method is preferably treated using a filtration device. This filtration treatment is a treatment for removing scales generated during the polymerization from the latex, and removing impurities or the like mixed from the raw material or from the outside during the polymerization. As the filtration device, a GAF filter system of ISP Filters PTA Ltd. using a bag-like mesh filter, a cylindrical filter medium is arranged on the inner surface of the cylindrical filter chamber, and a stirring blade is arranged in the filter medium A centrifugal filtration device or a vibration type filtration device in which the filter medium performs a horizontal circular motion and a vertical amplitude motion with respect to the filter medium surface is preferable.

  The rubber-containing polymer (x) can be produced by recovering the rubber-containing polymer (x) from the polymer latex produced by the above method. Examples of the method for recovering the rubber-containing polymer (x) from the polymer latex include salting out, acid precipitation coagulation, spray drying, freeze drying and the like. According to these methods, the rubber-containing polymer (x) is recovered in powder form.

<Acrylic (co) polymer (y)>
The acrylic (co) polymer (y) is derived from 50 to 100% by mass of a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, and other vinyl monomers copolymerizable therewith. A polymer composed of 0 to 50% by mass of the structural unit is preferred.

  Examples of other vinyl monomers copolymerizable with alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, and 2-ethylhexyl acrylate; carbon Alkyl methacrylate having an alkyl group of 5 or more; aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene; vinylcyan compounds such as acrylonitrile and methacrylonitrile, and the like, and one or more of these can be used .

  The polymerization method for obtaining the acrylic (co) polymer (y) is not particularly limited, and various methods such as a commonly known suspension polymerization method and emulsion polymerization method are applied.

  Examples of the acrylic (co) polymer (y) that can be preferably used include the Dainar BR series manufactured by Mitsubishi Rayon Co., Ltd. and the acrylpet manufactured by Mitsubishi Rayon Co., Ltd., which are commercially available.

<Acrylic resin>
The acrylic resin constituting the film is preferably composed of a mixture of the above-mentioned rubber-containing multistage polymer (x) and acrylic copolymer (y), or only composed of the rubber-containing multistage polymer (x). That is, in the acrylic resin, the ratio (mass ratio) of the rubber-containing multistage polymer (x) / acrylic (co) polymer (y) is 1/99 to 100/0, and the total of both is 100 parts by mass. It is necessary to be. In order to obtain sufficient strength, adhesion, and processability, the ratio (mass ratio) of the rubber-containing multistage polymer (x) / acrylic (co) polymer (y) is 10/90 to 100/0, The total of both is preferably 100 parts by mass.

  For acrylic resins, general compounding agents, such as stabilizers, lubricants, processing aids, plasticizers, impact aids, foaming agents, fillers, antibacterial agents, antifungal agents, mold release agents, as necessary An ultraviolet absorber may be added.

  It is preferable to extrude the acrylic resin directly or once into a pellet and then extrude it into a film.

  The thickness of the acrylic resin film is preferably in the range of 10 to 600 μm, but is more preferably in the range of 30 to 200 μm in consideration of ease of handling during transportation.

<Base material (C)>
The resin serving as the base material in the laminated molded body of the present invention is preferably one that can be melt bonded to the acrylic resin film. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, or a resin containing these as a main component can be given. In terms of adhesiveness, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin, acrylic resin or a resin containing these as a main component is preferable, and in particular, ABS resin, polycarbonate resin, acrylic resin, or a resin containing these as the main components is used. More preferred.

<Lamination method>
For the acrylic resin film on which the curable coating film of the present invention is laminated, a known method such as thermal lamination can be used for a base material that can be heat-sealed. It is possible to bond to a base material that is not heat-sealed through an adhesive. Moreover, well-known methods, such as an insert molding method and an in-mold molding method, can be used.

  Hereinafter, the present invention will be described in detail with reference to examples. For convenience, “parts by mass” is expressed as “parts” and “% by mass” is expressed as “%”.

[Synthesis Example 1]
Synthesis of Siloxane Compound (A1) As organosilanes, methyltrimethoxysilane (manufactured by Tama Chemical Industry Co., Ltd., molecular weight 136) 54.0 g, phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 198) to 6.0 g, 45.0 g of isopropyl alcohol was added and stirred to obtain a uniform solution. Furthermore, 45.0 g of water was added, and the mixture was heated at 80 ° C. for 3 hours with stirring to perform hydrolysis and condensation. Thereafter, the mixture was cooled to 25 ° C. and stirred for 24 hours to proceed the condensation, thereby obtaining 150 g of a siloxane compound (A1) solution having a solid content concentration of 20%. In addition, the solid content concentration in the present invention means a mass percentage with respect to the entire solution of the siloxane compound obtained when it is assumed that the hydrolysis and condensation are completely performed.

[Synthesis Example 2]
Synthesis of Siloxane Compound (A2) Methyl silicate with 53% silica conversion concentration as alkyl silicates (manufactured by Colcoat Co., average about 7 mer, average molecular weight about 789, trade name methyl silicate 53A) 10.0 g, methyl trimethoxysilane 10.0 g of isopropyl alcohol was added to 20.0 g (manufactured by Tama Chemical Industry Co., Ltd., molecular weight 136) and stirred to obtain a uniform solution. Furthermore, 10.0 g of water was added, and the mixture was heated at 80 ° C. for 3 hours with stirring to perform hydrolysis-condensation. Thereafter, the mixture was cooled to 25 ° C. and stirred for 24 hours to allow condensation to proceed. Furthermore, (gamma) -butyrolactone was added to make the whole 76.0g, and the solution of the siloxane compound (A2) of solid content concentration 20% was obtained.

[Synthesis Example 3]
Synthesis of surface-modified colloidal silica In a 300 ml eggplant-shaped flask equipped with a stirrer and a condenser, 100 g of isopropyl alcohol-dispersed colloidal silica (Snowtex IPA-ST-L) as colloidal silica (solid content 30 g), methyl as organoalkoxysilane 6.8 g (0.05 mol) of trimethoxysilane (manufactured by Tama Chemical Co., Ltd., molecular weight 136), 5.4 g (0.3 mol) of pure water and 54.5 g of isopropyl alcohol were charged, and 80 using a water bath Hydrolysis / condensation was carried out by heating and stirring at 0 ° C. for 3 hours to obtain a 20% solution of the condensate.

[Production Example 1]
Acrylic resin film (B1)
22 parts of rubber-containing polymer (x1) and MMA / MA copolymer as thermoplastic polymer (y1) (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g) To 78 parts, 0.1 part of “ADEKA STAB AO-60” manufactured by ADEKA was added as a compounding agent, and then mixed using a Henschel mixer. This resin composition was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets.

  The pellets produced by the above method were dried overnight at 80 ° C., and using a 40 mmφ non-vent screw type extruder (L / D = 26) fitted with a 300 mm wide T die, the cylinder temperature was 180-240 ° C., T An acrylic resin film having a thickness of 75 μm was formed under the condition of a die temperature of 240 ° C.

<Production of rubber-containing polymer (x1)>
In a polymerization vessel equipped with a reflux condenser, 310 parts of deionized water, an emulsifier (mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% and di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% sodium hydroxide mixture) (Partially neutralized product) 0.5 part, sodium carbonate 0.1 part, SFS (sodium formaldehyde sulfoxylate) 0.5 part, ferrous sulfate 0.00024 part and EDTA (ethylenediaminetetraacetate disodium) 0. 000072 parts of an aqueous solution was charged and the following first-stage monomer mixture was added dropwise at 80 ° C. over 200 minutes while stirring under a nitrogen atmosphere, and then polymerization was further performed for 120 minutes to obtain a latex of the polymer. . The Tg determined from the FOX formula of the polymer obtained by the polymerization of the monomer mixture in the first stage was -29 ° C.

  Next, an aqueous solution of 10 parts of deionized water and 0.15 part of SFS was added to the latex of this polymer, and the second-stage monomer of the following rubber-containing polymer (x1) was stirred under a nitrogen atmosphere. The mixture was added dropwise at 80 ° C. over 100 minutes, followed by further polymerization at 80 ° C. for 60 minutes to obtain a rubber-containing polymer (x1) latex. The Tg determined from the FOX equation of the polymer obtained by the polymerization of the second stage monomer mixture was 99 ° C.

  The rubber-containing polymer (x1) in the obtained polymer latex was measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. The diameter was 0.12 μm.

The polymer latex of the obtained rubber-containing polymer (x1) was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.5 parts of calcium acetate was added. Salting out was carried out in an aqueous solution, and the solid content was recovered by washing with water, followed by drying to obtain a powdery rubber-containing polymer (x1). The rubber-containing polymer (x1) had a gel content of 84% and a rubber content of 62.5%. The gel content is determined by extracting the rubber-containing polymer (x1) in an acetone solvent under reflux, separating the treated solution by centrifugation, and measuring the mass of acetone-insoluble matter after drying (mass after extraction). The following formula was used.
Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100

<First-stage monomer mixture>
n-BA (n-butyl acrylate) 81.0 parts St (styrene) 19.0 parts AMA (allyl methacrylate) 1.0 part tBH (t-butyl hydroperoxide) 0.25 parts Emulsifier 1.1 parts

<Second-stage monomer mixture>
MMA (methyl methacrylate) 57.0 parts MA (methyl acrylate) 3.0 parts n-OM (n-octyl mercaptan) 0.2 parts t-BH 0.1 part

[Production Example 2]
Acrylic resin film (B2)
100 parts of a rubber-containing polymer (x2), 2.1 parts of a product name “ADEKA STAB LA-31RG” manufactured by ADEKA, 0.1 part of a product name “ADEKA STAB AO-50” manufactured by ADEKA, and ADEKA After adding 0.3 part of the product name “Adeka Stab LA-57”, it was mixed using a Henschel mixer. This resin composition was supplied to a degassing extruder (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C. and kneaded to obtain pellets.

  The pellets produced by the above method were dried overnight at 80 ° C., and using a 40 mmφ non-vent screw type extruder (L / D = 26) fitted with a 300 mm wide T die, the cylinder temperature was 180-240 ° C., T An acrylic resin film having a thickness of 50 μm was formed under the condition of a die temperature of 240 ° C.

<Production of rubber-containing polymer (x2)>
After charging 8.5 parts of deionized water into a container equipped with a stirrer, 0.3 part of MMA, 4.5 parts of n-BA, 0.2 part of 1,3-BD (1,3-butylene glycol dimethacrylate), A monomer component consisting of 0.05 part of AMA and 0.025 part of CHP (cumene hydroperoxide) was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 186.5 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the first stage polymer (x2-k1). Subsequently, a monomer component consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Then, reaction was continued for 60 minutes and the polymer (x2-k) containing a 2nd step | paragraph polymer (x2-k2) was obtained. The Tg of the first stage polymer (x2-k1) alone was -48 ° C, and the Tg of the second stage polymer (x2-k2) alone was -48 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. A polymer (x2-1) was formed. The Tg of the third stage polymer (x2-1) alone was 20 ° C.

Subsequently, a monomer component consisting of 55.2 parts of MMA, 4.8 parts of n-BA, 0.19 part of n-OM and 0.08 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. The fourth-stage polymer (x2-m) was formed to obtain a polymer latex of the rubber-containing polymer (x2). The Tg of the fourth stage polymer (x2-m) alone was 84 ° C.
The weight-average particle diameter of the rubber-containing polymer (x2) measured after polymerization was 0.12 μm.

The polymer latex of the rubber-containing polymer (x2) obtained was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then an aqueous solution containing 3 parts of calcium acetate. Salting out was carried out, washed with water, collected, and dried to obtain a powdery rubber-containing polymer (x2).
The gel content of the rubber-containing polymer (x2) was 60%.

[Example 1]
[Preparation of curable composition]
250 g (solid content 50 g) of the target product (A1) of Synthesis Example 1 and 250 g (solid content 50 g) of the target product (A2) of Synthesis Example 2 were cured with a curing catalyst (San-Aid SI-100L, manufactured by Sanshin Chemical Industry Co., Ltd.). 4.0 g (solid content 2.0 g) was blended, and 0.5 g of a silicon-based surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent, 1-methoxy-2-propanol (PGM) 400 g was mixed to obtain a curable composition.

[Formation of film]
The acrylic resin film-like product (B1) obtained in Production Example 1 was coated on the 250 mm square with the curable composition described in Example 1 using a bar coater. Subsequently, the film was allowed to stand at 90 ° C. for 30 minutes in a hot air dryer, and the solvent was evaporated to form a coating film made of the curable composition. It was 18.7 when the FT-IR measurement of the coating film was performed.

In addition, the measurement of FT-IR is performed by a Fourier transform infrared absorption spectrometer (trade name: Nicolet 4700, manufactured by Nicorey, Inc.) equipped with a Thunder dome (used ATR crystal; Ge crystal, infrared light incident angle: 45 degrees) manufactured by Nicorey. ). The peak area derived from the siloxane bond, 960 cm ^{−1 to} 1240 cm ⁻¹ / peak area derived from Si—CH ₃ , 1250 cm ^{−1 to} 1300 cm ⁻¹ was calculated.

The film side of the film on which the obtained curable coating film was laminated was laminated on an acrylic base material (C) having a length of 250 mm, a width of 250 mm, and a thickness of 3 mm, and using a SUS press plate, a heating temperature of 130 ° C., It was pressed at a pressure of 7 MPa for 5 minutes, peeled off from the press plate and immediately placed on a wooden mold (R100) for molding. Furthermore, a high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., ultraviolet irradiation device, handy UV-1200, QRU-2161 type) was irradiated with ultraviolet rays of about 1,000 mJ / cm ² to obtain a cured film having a thickness of about 5 μm. It was. In addition, the ultraviolet irradiation amount was measured with an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-351 type, peak sensitivity wavelength 360 nm).

[Evaluation of coating]
The obtained molded body was evaluated by the following method.
1) Appearance The transparency of the acrylic plate having a cured coating and the presence or absence of whitening were observed with the naked eye and evaluated according to the following criteria.
○: Transparent and free from defects in whitening (good).
X: An opaque part or a defect such as whitening (defect).
2) Film thickness Measured with Metricon's MODEL 2010 PRISM COUPLER.
3) Workability The acrylic laminate having a cured coating formed on a wooden mold (R100) was visually observed for the presence of transparency, cracks, and whitening, and evaluated according to the following criteria.
○: Transparent and free from cracks and whitening defects (good).
X: An opaque part, a defect such as a crack or whitening (defect).

4) Film adhesion Adhesion to the cured film with a razor blade at 11mm intervals in 11mm lengths and widths to create 100 squares, with cellophane tape well adhered, and then peeled off rapidly 45 degrees forward The number of squares remaining without peeling off the cured film was measured and evaluated according to the following criteria.
◯: There are no peeled cells (good adhesion).
Δ: 1 to 5 peeled squares (medium adhesion).
X: Six or more squares peeled off (adhesion failure).
5) Abrasion resistance Using a wear wheel (manufactured by Calibrase: CS-10F), the cured coating was subjected to a 300-rotor Taber abrasion test at a load of 500 g, and the difference between the haze value after the Taber abrasion test and the haze value before the test ΔH (%).
○: 10% or less x: More than 10% 6) Crack resistance The molded body was left in hot water at a temperature of 90 ° C. for 2 hours, and the occurrence of cracks in the cured film was visually confirmed.
○: No crack was generated.
X: Cracks are generated.

  As a result, the cured coating film of this example had wear resistance, crack resistance, and good appearance.

  The evaluation results are shown in Table 1.

[Examples 2 and 3]
A cured film was obtained in the same manner as in Example 1 except that the materials listed in Table 1 were used. The evaluation results are shown in Table 1.

[Example 4]
A curable composition was obtained in the same manner as in Example 1 except that the materials shown in Table 1 were used. The curable composition described in Example 4 was coated on a 250 mm square acrylic resin film (B2) obtained in Production Example 2 with a bar coater. Subsequently, the film was allowed to stand at 30 ° C. for 60 minutes in a warm air dryer to evaporate the solvent, thereby forming a coating film made of the curable composition. The FT-IR measurement of the coating film was 18.2.

  The film side of the film on which the obtained curable coating film was laminated was laminated on an acrylic base material (C) having a length of 250 mm, a width of 250 mm, and a thickness of 3 mm, and using a SUS press plate, a heating temperature of 130 ° C., Preheating was performed for 5 minutes, pressing was performed at 130 ° C. and a pressure of 7 MPa for 5 minutes, and after peeling from the press plate, the mold was placed on a wooden mold (R100). The molded product was cured at 90 ° C. for 60 minutes with a warm air dryer to obtain a cured film. The evaluation results are shown in Table 1.

[Comparative Example 1]
The acrylic resin film-like product (B1) obtained in Production Example 1 was coated on the 250 mm square with the curable composition described in Example 1 using a bar coater. Subsequently, the mixture was left at 90 ° C. for 10 minutes in a hot air dryer to evaporate the solvent and form a curable resin layer.

Furthermore, a high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., ultraviolet irradiation device, handy UV-1200, QRU-2161 type) was irradiated with ultraviolet rays of about 1,000 mJ / cm ² to obtain a cured film having a thickness of about 5 μm. It was. In addition, the ultraviolet irradiation amount was measured with an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-351 type, peak sensitivity wavelength 360 nm). It was 22.5 when the FT-IR measurement of the coating film was performed.

  The film side of the film on which the curable coating film obtained by the above method is laminated is laminated on an acrylic base material (C) having a length of 250 mm, a width of 250 mm, and a thickness of 3 mm, and a heating temperature is used using a SUS press plate. Preheating was performed at 130 ° C. for 5 minutes, pressing was performed at 130 ° C. and a pressure of 7 MPa for 5 minutes. The evaluation results are shown in Table 1. In addition, since the crack had generate | occur | produced in the obtained hardened film surface, adhesiveness, abrasion resistance, and crack resistance were not evaluated.

[Comparative Example 2]
A cured film was obtained in the same manner as in Example 1 except that the drying conditions at the time of film formation were 90 ° C. and 5 minutes. It was 13.7 when the FT-IR measurement of the coating film was performed. The evaluation results are shown in Table 1. In addition, since the obtained cured film surface was not smooth, adhesiveness, abrasion resistance, and crack resistance were not evaluated.

[Comparative Example 3]
A cured film was obtained in the same manner as in Example 1 except that the acrylic coating agent shown in Table 1 was used instead of the siloxane compound and the initiator. The evaluation results are shown in Table 1.

Abbreviations in Table 1 are as follows.
A1: Siloxane compound A2 obtained in Synthesis Example 1 Siloxane compound SI-100L obtained in Synthesis Example 2: Photosensitive acid generator (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-100L)
L-7001: Silicone surfactant (manufactured by Dow Corning Toray, L-7001)
PGM: 1-methoxy-2-propanol acrylic coating agent: 60 parts of pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., M450), 40 parts of trimethylolpropane triacrylate (manufactured by Daiichi Kogyo Seiyaku, New Frontier TMPT), 1-hydroxy -Cyclohexylphenyl ketone 1.5 parts B1: Acrylic resin film B2 obtained in Production Example 1: Acrylic resin film substrate obtained in Production Example 2 (C): Acrylite (registered trademark) L manufactured by Mitsubishi Rayon 3mm

Claims (3)

Alkyl silicates represented by general formula (1)

(In the formula, R ¹ , R ² , R ³ and R ⁴ independently represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 20) Show.)
And organosilanes represented by the general formula (2)

(Wherein R ⁵ represents an organic group containing an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aryl group, an epoxy group, a (meth) acryloyl group, a mercapto group, an amino group, or an isocyanate group; R ⁶ represents an alkyl group having 1 to 5 carbon atoms, or an acyl group having 1 to 4 carbon atoms, and a represents an integer of 1 to 3). A curable coating film comprising a curable composition containing A) and having a ratio of the peak area derived from the siloxane bond in the infrared absorption spectrum / the peak area derived from Si—CH ₃ is 16 to 21 is laminated. Acrylic resin film (B)   The acrylic resin film (B) is composed of 100 parts by mass in total of 1 to 100 parts by mass of the rubber-containing multistage polymer (x) and 99 to 0 parts by mass of the acrylic (co) polymer (y). Acrylic resin film.   The molded object by which the acrylic resin film of Claim 1 or 2 was laminated | stacked on the base material (C).

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