JP5500355B2 - Decorative sheet for thermoforming and decorative molded product - Google Patents

Description

  The present invention relates to a thermoforming decorative sheet that can be used as an integrally molded decorative sheet for thermoforming and a decorative molded product using the same.

  As a method for decorating a resin molded body, in recent years, a method has been employed in which a decorative sheet that can be molded into a desired shape by heat is placed in a mold in advance, and the decorative sheet is applied simultaneously with the molding of the resin molded body. Yes. For example, an insert molding method (see, for example, Patent Document 1) in which an injection resin is filled on the back surface side of the decorative sheet after thermoforming and placed in contact with the concave mold of the injection mold, or a decorative sheet is vacuum formed. Vacuum molding simultaneous decorating method (for example, refer to Patent Document 2) formed by pasting and adhering to a three-dimensional adherend by a method, sheet molding compound (hereinafter abbreviated as SMC) or bulk molding compound (hereinafter referred to as BMC). In a heat compression molding method using a thermosetting resin composition containing reinforcing fibers, such as, a pattern layer is printed on a thermoplastic resin sheet having a melting temperature equal to or higher than the SMC molding temperature, and a nonwoven fabric is lined on this. A method of preparing a decorative sheet, laminating SMC so as to be in contact with the non-woven fabric side of the decorative sheet, and heating and pressurizing them in a mold (for example, patent document) 3), and a method in which an integrally molded decorative sheet for SMC in which a transparent resin layer, a decorative layer, and an adhesive layer are laminated in this order are stacked so as to be in contact with SMC and subjected to pressure thermoforming, and the like are known. (For example, refer to Patent Documents 4 and 5).

On the other hand, water-soluble members such as system kitchens, toilets, bathroom members, and the like are insoluble dirt such as water scale and soap residue. On the other hand, recently, the surface of the plastic molded body is processed to be hydrophilic, so that dirt or soap scum is difficult to adhere, or even if it adheres, dirt substances can be removed by simple cleaning operations such as washing with water. Means to do so have been introduced. For example, in Patent Document 6, on a surface material such as a nonwoven fabric or a woven fabric, a base layer formed using an acrylic polyol resin having an alkoxysilyl group as a coating material, an alkoxysilane compound, and at least one inorganic oxide are applied. A method is disclosed in which a decorative sheet provided with a surface layer formed using a surface layer coating material contained as a film material is integrated with SMC.
However, this method has a problem that it is inferior to oil-resistant soil, which is one of the indexes of contamination resistance.

Japanese Patent Laid-Open No. 08-267500 JP 2000-1553587 A JP-A-8-118384 Japanese Patent Laid-Open No. 11-207878 JP 2009-143047 A JP 2002-160320 A

  The problem to be solved by the present invention is to provide a decorative molded product that can exhibit hydrophilicity after thermoforming, and is excellent in antifouling property and durability, and heat that can provide such a decorative molded product. An object is to provide an integrally molded decorative sheet using a molding sheet.

  As a result of intensive studies, the present inventors have provided a cured product layer of a polysiloxane resin having a specific siloxane bond on the surface of a base sheet, and an integrated mold having a sulfur trioxide-containing gas in contact with the cured product layer. It has been found that a decorative sheet for thermoforming can solve the above problems.

  That is, the present invention provides a polysiloxane segment having a structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group provided on a base sheet. A cured product of a resin composition containing a composite resin (A) in which (a1) and a vinyl polymer segment (a2) are bonded by a bond represented by the general formula (3) A decorative sheet for thermoforming that is surface-treated with gas is provided.

（１）

(1)

（２）

(2)

(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (where R ⁴ is A single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or an aralkyl having 7 to 12 carbon atoms. Represents a group.)

（３）

(3)

(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do)

  The present invention also provides a decorative molded product obtained by superposing the above-described thermoforming decorative sheet so as to be in contact with the sheet molding compound and pressurizing and thermoforming the sheet.

  The present invention also provides a decorative molded product obtained by mounting the above-described decorative sheet for thermoforming in an injection mold and injection molding.

  Moreover, this invention provides the decorative molded product obtained by affixing the said decorative sheet for thermoforming to the to-be-adhered body by the vacuum forming method, and integrating.

According to the present invention, it is possible to obtain a decorative molded product that can exhibit hydrophilicity even after thermoforming and is excellent in antifouling property and durability.
The decorative sheet for thermoforming of the present invention uses a sulfonation treatment as a method for imparting hydrophilicity, can exhibit hydrophilicity even after thermoforming, and is particularly excellent in durability to oil. In particular, the composite resin (A) has an advantage that it is particularly excellent in alkali resistance of a coating film obtained because it has a bond represented by the general formula (3).

  Further, by using the composite resin (A) in combination with a crosslinkable monomer such as an isocyanate or an acrylic monomer, the crosslink density is increased, and surface physical properties with more excellent scratch resistance can be obtained.

In addition, the presence of an aryl group in the resin composition can further enhance the sulfonation effect and obtain surface properties with more excellent antifouling properties. In particular, since any of R ¹ , R ² and R ³ in the general formula (1) in the composite resin (A) is an aryl group, that is, a structure in which an aryl group is directly bonded to a silicon atom, sulfonation Stable antifouling property is obtained because it is difficult to be decomposed during processing.

  In addition, the decorative sheet for thermoforming of the present invention can be preferably used as a decorative sheet for thermoforming of an SMC integrated mold, and obtained by superposing and pressing the sheet so as to be in contact with the sheet molding compound. A decorative molded product can be provided.

  The decorative sheet for thermoforming according to the present invention can be preferably used as a decorative sheet for thermoforming of an integral molding die for injection molding, and is obtained by mounting the sheet in an injection mold and injection molding. A decorative molded product can be provided.

  Moreover, the decorative sheet for thermoforming of the invention can be preferably used as a decorative sheet for thermoforming of a vacuum forming simultaneous mold, and the decorative sheet obtained by attaching the sheet to an adherend by a vacuum forming method and integrating it. Can provide molded products.

(Substrate sheet)
The base material sheet used in the present invention varies depending on the thermoforming method used, but a thermoplastic resin sheet is preferable if used for the injection molding (insert molding) method or the vacuum molding simultaneous decorating method. If used for thermoforming, a non-woven fabric, a woven fabric, a thermoplastic resin sheet, a decorative prepreg sheet obtained by semi-curing a thermosetting resin, and the like can be used.

(Thermoplastic resin sheet)
The thermoplastic resin sheet is not particularly limited, and any thermoplastic resin sheet that is usually used for thermoforming can be used. Moreover, it is a single layer or a multilayer film, and may contain coloring agents, such as a pigment or dye.
Specifically, the sheet is mainly composed of a thermoplastic resin having a softening point in the range of 30 to 300 ° C. in order to perform the molding step by heat, and a preferable softening point is in the range of 50 to 250 ° C.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, ionomer resins, polystyrene, polyacrylonitrile and acrylonitrile. -Styrene resin, methyl methacrylate-styrene resin, polyacrylonitrile, polyamide resin such as nylon 6 and nylon 66, ethylene-vinyl acetate, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride, Chlorine resin such as polyvinylidene chloride, fluorine resin such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resin, cyclic polyolefin Fin, modified polyphenylene ether resins, methylpentene resins, cellulose resins are preferably used. Among these thermoplastic resins, a sheet mainly composed of at least one selected from the group consisting of acrylic resin, polyester resin, polycarbonate resin, and polyolefin resin is preferable because it is excellent in thermoformability and metal design. .
These blends and polymer alloys can be used as long as the transparency of the sheet is not impaired. These may be used in a single layer or multiple layers.
Moreover, these thermoplastic resin sheets are good also as a rubber modified body. There is no particular limitation on the method of making the rubber modified, but a method of copolymerizing by adding a rubber component monomer such as butadiene at the time of polymerization of each resin, and hot melting of each resin and synthetic rubber or thermoplastic elastomer. The method of blending is mentioned.

  The method for producing the thermoplastic resin sheet is not particularly limited, and may be formed into a sheet by a conventional method. Further, the thermoplastic resin sheet may be stretched in a uniaxial or biaxial direction as long as the spreadability during thermoforming is not hindered.

In addition, conventional additives may be added to these thermoplastic resin sheets as long as the moldability is not hindered. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants , Antiozonants, activators, antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants and additives You may mix | blend additives, such as a flow promoter and a flow promotion adjuvant. These additives may be used alone or in combination of two or more.
The thickness of the thermoplastic resin sheet is not particularly limited, but a sheet having a thickness of about 0.1 mm to 0.5 mm is preferably used.

  When decorating the nonwoven fabric, woven fabric, or thermoplastic resin sheet surface, a pattern such as a wood grain pattern, a stone pattern, or a geometric pattern is formed mainly by printing. As a printing method of this pattern, any method such as letterpress printing, intaglio (gravure) printing, offset printing, silk printing and the like may be used. Further, instead of direct printing, an arbitrary peelable film provided with the printing layer and the non-woven fabric, woven fabric, or thermoplastic resin sheet may be overlapped and bonded together by dry lamination (dry lamination method).

(Resin composition Composite resin (A))
The composite resin (A) used in the present invention is a polysiloxane having a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. Segment (a1) (hereinafter simply referred to as polysiloxane segment (a1)) and vinyl polymer segment (a2) having alcoholic hydroxyl group (hereinafter simply referred to as vinyl polymer segment (a2)) This is a composite resin (A) bonded by a bond represented by formula (3).

The silanol group and / or hydrolyzable silyl group possessed by the polysiloxane segment (a1) described later and the silanol group and / or hydrolyzable silyl group possessed by the vinyl polymer segment (a2) described below undergo a dehydration condensation reaction. Thus, the bond represented by the general formula (3) is generated. Accordingly, in the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). And
The form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2). And a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded.

(Composite resin (A) Polysiloxane segment (a1))
The polysiloxane segment (a1) in the present invention is a segment having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group.

(Structural unit represented by general formula (1) and / or general formula (2))
Specifically, R ¹ , R ² and R ³ in the general formulas (1) and (2) are each independently —R ⁴ —CH═CH ₂ , —R ⁴ —C (CH ₃ ) = A group having one polymerizable double bond selected from the group consisting of CH ₂ , —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ , and —R ⁴ —O—CO—CH═CH ₂ ( R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 to 7 carbon atoms. 12 aralkyl groups are represented.

Examples of the alkylene group having 1 to 6 carbon atoms in R ⁴ include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, and pentylene. Group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene Group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1, 2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2-methyl Examples include a propylpropylene group and a 1-ethyl-1-methylpropylene group. Among these, R ⁴ is preferably a single bond or an alkylene group having 2 to 4 carbon atoms because of easy availability of raw materials.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2 , 2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, and the like.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In the present invention, when at least one of R ¹ , R ² and R ³ is the aryl group, that is, since it has a structure in which an aryl group is directly bonded to a silicon atom, it is difficult to be decomposed during the sulfonation treatment. The antifouling property obtained is preferable. The aryl group is a group having a high effect of the sulfonation treatment, and is directly bonded to the silicon atom, so that decomposition during the sulfonation treatment and desulfonation after the sulfonation treatment hardly occur. Therefore, deterioration of the coating film appearance due to decomposition is suppressed, and the hydrophilization ability continues for a long time.
When at least one of R ¹ , R ² and R ³ is an aryl group, specifically, when the polysiloxane segment (a1) has only the structural unit represented by the general formula (1), R ^{When 1} is an aryl group and the polysiloxane segment (a1) has only the structural unit represented by the general formula (2), R ² and / or R ³ is an aryl group, and the polysiloxane segment (a1) When has both the structural units represented by the general formula (1) and the general formula (2), it indicates that at least one of R ¹ , R ² and R ³ is an aryl group.

Further, when at least one of R ¹ , R ² and R ³ is a group having the polymerizable double bond, it can be cured by an active energy ray or the like, and an active energy ray and a silanol group and / or The two curing mechanisms of improving the crosslinking density of the coating film by the condensation reaction of hydrolyzable silyl groups can form a cured coating film with better scratch resistance, acid resistance, alkali resistance and solvent resistance, and thermosetting It is difficult to use a functional resin composition, and it can be suitably used for a base material that easily undergoes thermal deformation, such as a paint for building exteriors and plastics.
It is preferable that two or more groups having a polymerizable double bond exist in the polysiloxane segment (a1), more preferably 3 to 200, more preferably 3 to 50, A coating film having more excellent scratch resistance can be obtained. Specifically, when the content of the polymerizable double bond in the polysiloxane segment (a1) is 3 to 35% by weight, desired wear resistance can be obtained. The polymerizable double bond here is a general term for groups capable of performing a growth reaction by free radicals among vinyl group, vinylidene group or vinylene group. Moreover, the content rate of a polymerizable double bond shows the weight% in the polysiloxane segment of the said vinyl group, vinylidene group, or vinylene group.
As the group having a polymerizable double bond, all known functional groups containing the vinyl group, vinylidene group, and vinylene group can be used. Among them, —R ⁴ —C (CH ₃ ) = The (meth) acryloyl group represented by CH ₂ or —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ is rich in reactivity at the time of ultraviolet curing, and a vinyl polymer segment (described later) The compatibility with a2) is favorable, and a cured coating film having excellent transparency is obtained, which is preferable.

  The structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a three-dimensional network structure is formed but a dense network structure is not formed, gelation or the like does not occur during production or primer formation, and the storage stability is improved.

(Composite resin (A) Silanol group and / or hydrolyzable silyl group)
In the present invention, the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is a silanol group formed by combining an oxygen atom having a bond with a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2). Preferably there is.

  In the present invention, the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (4). .

（４）

(4)

(In the general formula (4), R ⁵ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁶ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, (It is a hydrolyzable group selected from the group consisting of an amino group, an amide group, an aminooxy group, an iminooxy group and an alkenyloxy group, and b is an integer of 0 to 2.)

Examples of the alkyl group in R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert group. -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.
Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy and the like.
Examples of the aryloxy group include phenyloxy and naphthyloxy.
Examples of the alkenyloxy group include a vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2 -A hexenyloxy group etc. are mentioned.

By hydrolyzing the hydrolyzable group represented by R ⁶ , the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group. Among these, a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.
The hydrolyzable silyl group specifically includes an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) bonded to the hydrolyzable group. Or it is preferable that it is the hydrolyzable silyl group substituted.

Since the silanol group or the hydrolyzable silyl group undergoes a hydrolytic condensation reaction between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group, the polysiloxane structure of the resulting coating film The crosslink density increases, and a coating film excellent in solvent resistance can be formed.
Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group is bonded to the vinyl polymer segment (a2) described later via the bond represented by the general formula (3). Use when.

The polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. Other groups may be included. For example,
A polysiloxane segment (a1) in which a structural unit in which R ¹ in the general formula (1) is an aryl group and a structural unit in which R ¹ in the general formula (1) is an alkyl group such as methyl coexist. It ’s good,
In the general formula (1), R ¹ is a group having a polymerizable double bond, a structural unit in which R ¹ in the general formula (1) is an aryl group, and in the general formula (2) It may be a polysiloxane segment (a1) in which R ² and R ³ coexist with a structural unit that is an alkyl group such as a methyl group,
A structural unit in which R ¹ in the general formula (1) is a group having a polymerizable double bond coexists with a structural unit in which either R ² or R ³ in the general formula (2) is an aryl group. The polysiloxane segment (a1) may be used and is not particularly limited.
Specifically, examples of the structure in which at least one of R ¹ , R ² and R ³ is the aryl group as the polysiloxane segment (a1) include the following structures.

In addition, examples of the structure in which at least one of R ¹ , R ^2, and R ³ is a group having the polymerizable double bond as the polysiloxane segment (a1) include the following structures.

  In the present invention, the polysiloxane segment (a1) is preferably contained in an amount of 10 to 65% by weight based on the total solid content of the resin composition, and both the scratch resistance and the properties of adhesion to a substrate such as plastic are made compatible. Is possible.

(Composite resin (A) vinyl polymer segment (a2))
The vinyl polymer segment (a2) in the present invention is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer. . These are preferably selected appropriately depending on the application. For example, an acrylic polymer segment is preferable when it is desired to obtain transparency and gloss of the surface layer to be obtained, and an aromatic vinyl polymer segment is preferable when hydrophilicity is imparted by sulfonation.

  The acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer. The (meth) acrylic monomer is not particularly limited, and vinyl monomers can also be copolymerized. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate and lauryl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ω-alkoxyalkyl such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate ( ) Acrylates; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and other carboxylic acid vinyl esters; methyl crotonate, alkyl crotonate and other alkyl esters; dimethyl malate, di-n -Dialkyl esters of unsaturated dibasic acids such as butyl malate, dimethyl fumarate and dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene and the like Fluoroolefins; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) Acrylamide, N- (meth) acryloyl morpholine, N- (meth) acryloyl pyrrolidine, tertiary amide group-containing monomers such as N- vinylpyrrolidone and the like.

  The aromatic vinyl polymer segment is obtained by polymerizing or copolymerizing aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene and the like. When copolymerizing, the (meth) acrylic monomer is preferably copolymerized.

  There are no particular limitations on the polymerization method, solvent, or polymerization initiator for copolymerizing the monomers, and the vinyl polymer segment (a2) can be obtained by a known method. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di- The vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate or the like.

  The number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn), and the composite resin (A) is produced. It is possible to prevent thickening and gelation during the process and to have excellent durability. Among these, Mn is more preferably in the range of 700 to 100,000, and the range of 1,000 to 50,000 is still more preferable for the reason that a good film can be formed when a layer is formed on the substrate.

  In addition, the vinyl polymer segment (a2) is a vinyl polymer segment (A) in order to form a composite resin (A) bonded by the bond represented by the general formula (3) with the polysiloxane segment (a1). It has a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon bond in a2). Since these silanol groups and / or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (A) described later, the composite resin (A ) In the vinyl polymer segment (a2). However, there is no problem even if silanol groups and / or hydrolyzable silyl groups remain in the vinyl polymer segment (a2), and when the coating film is formed by the curing reaction of the group having a polymerizable double bond. In parallel with the curing reaction, a hydrolysis condensation reaction proceeds between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group, so that the crosslink density of the polysiloxane structure of the resulting coating film And a coating film excellent in solvent resistance can be formed.

Specifically, the vinyl polymer segment (a2) having a silanol group directly bonded to a carbon bond and / or a hydrolyzable silyl group includes the above-mentioned general-purpose monomer, and a silanol group bonded directly to a carbon bond and / or It is obtained by copolymerizing a vinyl monomer containing a hydrolyzable silyl group.
Examples of vinyl monomers containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri (2-methoxyethoxy) silane. , Vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyl Examples include methyldimethoxysilane and 3- (meth) acryloyloxypropyltrichlorosilane. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

Moreover, when containing crosslinking agents, such as below-mentioned polyisocyanate, it is preferable that the said vinyl polymer segment (a2) has reactive functional groups, such as alcoholic hydroxyl group. For example, the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acrylic monomer having an alcohol hydroxyl group. Specific examples of the (meth) acrylic monomer having an alcohol hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono Various α such as butyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, “Placcel FM or Plaxel FA” [Caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.] Hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid or an adduct thereof with ε- caprolactone, and the like.
Of these, 2-hydroxyethyl (meth) acrylate is preferable because it is easy to react.

  It is preferable that the amount of the alcoholic hydroxyl group is appropriately determined by calculating from the amount of polyisocyanate to be described later.

(Production method of composite resin (A))
Specifically, the composite resin (A) used in the present invention is produced by the methods shown in the following (Method 1) to (Method 3).

(Method 1) Directly bonded to a carbon bond by copolymerizing the general-purpose (meth) acrylic monomer and the like and a vinyl monomer containing a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon bond. A vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group is obtained. This and a silane compound are mixed and hydrolytic condensation reaction is carried out. When there is a group to be introduced, a silane compound having the group to be introduced is used. For example, when an aryl group is introduced, a silane compound having both an aryl group and a silanol group and / or a hydrolyzable silyl group may be used as appropriate. When a group having a polymerizable double bond is introduced, a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group may be used.
In the method, the silanol group or hydrolyzable silyl group of the silane compound and the silanol group contained in the vinyl polymer segment (a2) containing the silanol group and / or hydrolyzable silyl group directly bonded to the carbon bond and In addition, a hydrolytic condensation reaction with a hydrolyzable silyl group forms the polysiloxane segment (a1), and the polysiloxane segment (a1) and the vinyl polymer segment (a2) have the general formula. The composite resin (A) combined by the bond represented by (3) is obtained.

(Method 2) In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
On the other hand, a silane compound (when there is a group to be introduced, a silane compound having the group to be introduced is used) undergoes a hydrolytic condensation reaction to obtain a polysiloxane segment (a1). Then, the silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) and the silanol group and / or hydrolyzable silyl group of the polysiloxane segment (a1) are subjected to a hydrolytic condensation reaction. Let

  (Method 3) Similarly to Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained. On the other hand, the polysiloxane segment (a1) is obtained in the same manner as in Method 2. Further, if necessary, a silane compound having a group to be introduced is mixed and subjected to a hydrolysis condensation reaction.

  Specific examples of the silane compound having both an aryl group and a silanol group and / or a hydrolyzable silyl group used in introducing the aryl group in the above (Method 1) to (Method 3) include phenyltrimethoxy. Various organotrialkoxysilanes such as silane and phenyltriethoxysilane; various diorganodialkoxysilanes such as diphenyldimethoxysilane and methylphenyldimethoxysilane; chlorosilanes such as phenyltrichlorosilane and diphenyldichlorosilane . Among them, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo hydrolysis reaction and easily remove by-products after the reaction can be used.

  In addition, as a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group used when introducing a group having a polymerizable double bond, for example, vinyltrimethoxy Silane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane and the like are used in combination. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

  In addition, as general-purpose silane compounds used in the (Method 1) to (Method 3), for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n- Various organotrialkoxysilanes such as propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane Or various diorganodialkoxysilanes such as methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or the like. Roshiran acids and the like. Of these, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo a hydrolysis reaction and easily remove by-products after the reaction are preferable.

  In addition, a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can. When the tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 with respect to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use together so that it may become the range which does not exceed mol%.

  In addition, a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired. For example, it is preferable to use the metal alkoxide compound in combination in a range not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).

  In the hydrolysis condensation reaction in the (Method 1) to (Method 3), a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups or the hydroxyl group and the hydrolysis are hydrolyzed. This refers to a proceeding condensation reaction that proceeds with a functional group. The hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable.

  Examples of the catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds containing various basic nitrogen atoms, such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium Quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetate Examples thereof include tin carboxylates such as narate, tin octylate and tin stearate. A catalyst may be used independently and may be used together 2 or more types.

  The amount of the catalyst to be added is not particularly limited, but generally it is preferably used in the range of 0.0001 to 10% by weight with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.001 to 1% by weight.

The amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water.

  The reaction temperature for carrying out the hydrolytic condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C to 150 ° C, and preferably in the range of 20 ° C to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced | generated in the said hydrolysis-condensation reaction by methods, such as distillation, as needed.

  The charging ratio of each compound in the (Method 1) to (Method 3) is appropriately selected depending on the desired structure of the composite resin (A) used in the present invention. Especially, since the durability of the obtained coating film is excellent, it is preferable to obtain the composite resin (A) such that the content of the polysiloxane segment (a1) is 30 to 95% by weight, and 30 to 75% by weight. Further preferred.

  In the above (Method 1) to (Method 3), as a specific method for conjugating the polysiloxane segment and the vinyl polymer segment in a block form, the above-mentioned silanol group and For example, in the case of (Method 1), a silane compound is mixed with the vinyl polymer segment, and a hydrolyzable silyl group-containing vinyl polymer segment is used as an intermediate. The method of carrying out decomposition condensation reaction is mentioned.

  On the other hand, in the above (Method 1) to (Method 3), as a specific method of complexing the polysiloxane segment to the vinyl polymer segment in a graft form, the main chain of the vinyl polymer segment is The vinyl polymer segment having a structure in which silanol groups and / or hydrolyzable silyl groups are randomly distributed is used as an intermediate. For example, in the case of (Method 2), the vinyl polymer segment is Examples thereof include a method of subjecting the silanol group and / or hydrolyzable silyl group and the silane compound to a hydrolytic condensation reaction.

(Resin composition Other resins having an aryl group)
Use of the composite resin (A) in combination with an acrylic resin or styrene resin having an aryl group is preferable because the hydrophilicity of the surface-treated substrate can be further increased. As such a resin, an aromatic vinyl polymer used as the vinyl polymer segment (a2) used in the composite resin (A) can be used. An aromatic vinyl polymer having a number average molecular weight in the range of 1000 to 10,000 is preferable because a good film can be formed when a layer is formed on a substrate. The number of aryl groups varies depending on the desired degree of hydrophilicity, but is preferably 5.0 to 60 mol%.

(Resin Composition Polyisocyanate (B))
By introducing a reactive functional group into the composite resin (A) and using a crosslinking agent or the like in combination, a layer having a higher degree of crosslinking and excellent weather resistance and scratch resistance can be obtained. As the crosslinking agent, polyisocyanate (B) is preferable, and in that case, it is preferable that the vinyl polymer segment (a2) in the composite resin (A) has an alcoholic hydroxyl group. The polyisocyanate (B) at that time is preferably contained in an amount of 5 to 50% by weight based on the total solid content of the active energy ray-curable resin layer. By containing the polyisocyanate (B) in this range, a coating film having particularly excellent long-term weather resistance (specifically, crack resistance) outdoors can be obtained. This is because the polyisocyanate reacts with a hydroxyl group in the system (this is a hydroxyl group in the active energy ray-curable monomer having a hydroxyl group in the vinyl polymer segment (a2) or an alcoholic hydroxyl group described later). Thus, it is estimated that a urethane bond, which is a soft segment, is formed and functions to relieve stress concentration due to curing derived from a polymerizable double bond.

  The polyisocyanate (B) to be used is not particularly limited and known ones can be used, but aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, Since polyisocyanates mainly composed of aralkyl diisocyanates such as α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate have a problem that a cured coating film is yellowed after long-term outdoor exposure. It is preferable to minimize the amount used.

  From the viewpoint of long-term outdoor use, the polyisocyanate used in the present invention is preferably an aliphatic polyisocyanate containing an aliphatic diisocyanate as a main raw material. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4). ) -Trimethyl-1,6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane, 1,3-bis (diisocyanate methyl) cyclohexane, 4, Examples include 4′-dicyclohexylmethane diisocyanate. Among these, HDI is particularly suitable from the viewpoint of crack resistance and cost.

  Examples of the aliphatic polyisocyanate obtained from the aliphatic diisocyanate include allophanate type polyisocyanate, biuret type polyisocyanate, adduct type polyisocyanate, and isocyanurate type polyisocyanate, and any of them can be suitably used.

  In addition, as the above-described polyisocyanate, so-called blocked polyisocyanate compounds blocked with various blocking agents can be used. Examples of the blocking agent include alcohols such as methanol, ethanol and lactic acid esters; phenolic hydroxyl group-containing compounds such as phenol and salicylic acid esters; amides such as ε-caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketoxime Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate and acetylacetone can be used.

The isocyanate group in the polyisocyanate (B) is preferably 3 to 30% by weight from the viewpoint of crack resistance and wear resistance of the resulting cured coating film. When the isocyanate group in the polyisocyanate (B) is more than 30%, the molecular weight of the polyisocyanate is decreased, and crack resistance due to stress relaxation may not be exhibited.
The reaction between the polyisocyanate and a hydroxyl group in the system (this is a hydroxyl group in the active energy ray-curable monomer having a hydroxyl group in the vinyl polymer segment (a2) or an alcoholic hydroxyl group described below), There is no need for heating, etc., and the reaction proceeds gradually by leaving it at room temperature. If necessary, the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80 ° C. for several minutes to several hours (20 minutes to 4 hours). In that case, you may use a well-known urethanation catalyst as needed. The urethanization catalyst is appropriately selected according to the desired reaction temperature.

(Resin composition and other compounds)
The resin composition used in the present invention can be cured by active energy rays when the composite resin (A) contains a group having the aforementioned polymerizable double bond. Active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, or electron beams usually extracted from particle accelerators of 20 to 2000 kV, Examples include α rays, β rays, γ rays, and the like. Of these, ultraviolet rays or electron beams are preferably used. In particular, ultraviolet rays are suitable. As the ultraviolet ray source, sunlight, low-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, argon laser, helium / cadmium laser, or the like can be used. Using these, the coating film can be cured by irradiating the coated surface of the active energy ray-curable resin layer with ultraviolet rays having a wavelength of about 180 to 400 nm. The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.
Curing with active energy rays is particularly effective when the substrate is a material with poor heat resistance, such as plastic. On the other hand, when heat is used in a range that does not affect the substrate, a known heat source such as hot air or near infrared rays can be used.

When curing with ultraviolet rays, it is preferable to use a photopolymerization initiator. Known photopolymerization initiators may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins include benzoin, benzoin methyl ether, and benzoin isopropyl ether. A photoinitiator (B) may be used independently and may use 2 or more types together.
The amount of the photopolymerization initiator (B) used is preferably 1 to 15% by weight and more preferably 2 to 10% by weight with respect to 100% by weight of the composite resin (A).

Moreover, it is preferable to contain an active energy ray hardening monomer as needed, especially polyfunctional (meth) acrylate. Polyfunctional (meth) acrylates are not particularly limited, and known ones can be used. For example, 1,2-ethanediol diacrylate, 1,2-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, Tripropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tris (2-acryloyloxy) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, di (penta Erythritol) pentaacrylate, di (pentaerythritol) hexaacrylate, etc. have two or more polymerizable double bonds in one molecule That polyfunctional (meth) acrylate. Moreover, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can be illustrated as polyfunctional acrylate. These may be used alone or in combination of two or more.
For example, when the above-described polyisocyanate is used in combination, an acrylate having a hydroxyl group such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate is preferable. In order to further increase the crosslinking density, it is also effective to use a (meth) acrylate having a particularly high functional group number such as di (pentaerythritol) pentaacrylate or di (pentaerythritol) hexaacrylate.

  In addition, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, “Plexel” manufactured by Daicel Chemical Industries), phthalic acid and propylene Mono (meth) acrylate of polyester diol obtained from glycol, mono (meth) acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol Tri (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, (meth) acrylate of various epoxy esters Hydroxyl group-containing (meth) acrylic acid esters such as phosphoric acid adducts; carboxyl group-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; vinyl sulfonic acid, styrene sulfone Sulfonic acid group-containing vinyl monomers such as acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3- Examples thereof include acidic phosphate ester vinyl monomers such as chloro-propyl acid phosphate and 2-methacryloyloxyethylphenyl phosphoric acid; vinyl monomers having a methylol group such as N-methylol (meth) acrylamide. These can use 1 type (s) or 2 or more types. Considering the reactivity of the polyfunctional isocyanate (b) with the isocyanate group, the monomer (c) is particularly preferably a (meth) acrylic acid ester having a hydroxyl group.

  The amount used when the polyfunctional acrylate is used is preferably 1 to 85% by weight, more preferably 5 to 80% by weight, based on the total solid content of the resin composition used as the active energy ray-curable resin layer. . By using the polyfunctional acrylate within the above range, physical properties such as hardness of the resulting layer can be improved.

  On the other hand, in the case where thermosetting is used in combination, each catalyst is considered in consideration of the reaction temperature, reaction time, etc. of the polymerizable double bond reaction in the composition and the urethanization reaction between the alcoholic hydroxyl group and the isocyanate. It is preferable to select. Moreover, it is also possible to use a thermosetting resin together. Examples of the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, and modified resins thereof.

  Other organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, UV absorbers, antioxidants as necessary Alternatively, various additives such as a plasticizer can also be used.

(Method for manufacturing a decorative sheet for thermoforming)
The method of providing the resin composition layer on the base sheet is a flow coater, roll coater, spraying method, airless spray method, air spray method, brush coating, roller coating, trowel coating, dipping method, pulling method, nozzle method, Examples thereof include a winding method, a sink method, a laying method, a patching method, and the like. When the base sheet has a printed layer, the resin composition layer is provided on the printed layer or on the opposite side of the base sheet from the side on which the printed layer is provided.

  It becomes a hardened | cured material layer by hardening the said resin composition layer by arbitrary methods. Since the composite resin (A) has a silanol group and / or a hydrolyzable silyl group, it reacts gradually even at room temperature to form a cured product layer, but it is preferably heated to accelerate the reaction. Moreover, when the said composite resin (A) has group which has a polymerizable double bond, it is preferable to harden | cure by active energy ray hardening. Moreover, also when it contains polyisocyanate (B), it is preferable to make it harden | cure by heating.

  The film thickness of the resin composition layer is preferably 0.1 to 300 μm because a cured coating film having excellent scratch resistance can be formed.

(Surface treatment using sulfur trioxide-containing gas)
A sulfur trioxide-containing gas is brought into contact with the cured product layer of the resin composition layer provided on the substrate sheet by a known method.
There is no particular limitation on the sulfur trioxide gas, but the gas supply source is generated by gasifying liquid stabilized sulfur trioxide (boiling point 44.8 ° C), vaporizing from fuming sulfuric acid, and burning sulfur in air. For example, use of sulfur trioxide gas obtained by catalytic oxidation of the sulfur dioxide gas produced is used.
Also, the dilution drying gas that is usually used is a drying gas that does not react with sulfur trioxide, and specifically includes an inert gas such as dry nitrogen, helium, and argon, and dry air. Then, it is desirable to use dry air. It is preferable that this sulfur trioxide containing gas is heated, Preferably it is the range of 40-120 degreeC, More preferably, it is 40-100 degreeC.

  The concentration of sulfur trioxide gas is preferably 0.1 to 10% by volume, more preferably 0.1 to 5% by volume. If the amount is less than 0.1% by volume, surface modification may not be sufficiently performed. If it exceeds 10% by volume, the cured product layer tends to deteriorate due to the resin composition.

  The atmospheric temperature in the container when contacting with the base material having a cured product layer made of sulfur trioxide-containing gas and resin composition depends on the material of the base material to be modified, but is preferably in the range of 20 ° C to 120 ° C. More preferably, it is 30 to 100 ° C. If it is less than 20 ° C., surface modification may not be sufficiently performed. If the temperature exceeds 120 ° C., the resin composition layer tends to deteriorate.

  The contact time between the sulfur trioxide-containing gas and the base material sheet having a cured product layer of the resin composition is preferably in the range of 1 minute to 120 minutes, although it depends on the type of the base material. The range of -30 minutes is more preferable, and more preferably 5-20 minutes. If it is less than 1 minute, surface modification may not be performed sufficiently, and fluctuations in product quality may increase. If it exceeds 120 minutes, the cured product layer tends to deteriorate due to the resin composition.

  Although it does not restrict | limit especially as a supply method of sulfur trioxide containing gas, For example, a sulfur trioxide containing gas may be distribute | circulated continuously to one direction, and the gas after distribution | circulation may be sent to an exhaust gas treatment apparatus. Alternatively, external circulation may be performed using an air supply fan or the like. The gas flow rate at this time depends on the internal volume of the processing container, and is preferably 0.5 to 10 times the volume of the processing container per minute. More preferably, the amount is 1 to 5 times. Alternatively, after reducing the pressure in the previous step 2, the pressure may be returned to normal pressure with the mixed gas, and the gas may not be circulated and may be kept sealed. For example, in the case of a flow type, if the container has an internal volume of 2 liters (L), the gas flow rate is 1 L / min to 20 L / min.

  In terms of quality, it is preferable to control the amount of water in the reaction vessel. For example, it is preferable to remove the moisture in the processing container of the base material having the resin composition layer to be modified, or to control the moisture content of the sulfur trioxide-containing gas to be used. The amount of water inside the reaction vessel can be controlled by tracking the dew point or the amount of water of the replacement gas discharged from the container or with a dew point meter such as a polymer thin film type. The target for the dew point is preferably −50 ° C. or lower, and more preferably −60 ° C. or lower.

  The sulfur atom content on the surface of the cured product layer obtained by the resin composition thus obtained is preferably in the range of 0.1 to 10% by number of sulfur atoms as measured by an X-ray photoelectron spectrometer. The range of 1.0 to 6.0 sulfur atom number% is more preferable.

  Further, in the present invention, it is preferable that after the contact, an immediate post-treatment is performed to remove sulfur trioxide or sulfuric acid remaining on the surface. Examples of the post-treatment method include washing with water, treatment with an aqueous solution of sodium bicarbonate and lime water, and the like. It is preferable to wash with ion exchange water at 10 ° C. or higher after washing with an alkaline solution. As the alkali ion component of the alkaline solution, ammonium ion, sodium ion, copper ion, silver ion and the like are preferable.

  In the present invention, a hydrophilic treatment can be selectively performed by masking a portion that does not require a surface treatment. A known method is used as the masking method. For example, resin or paper film with adhesive, paper, masking with metal foil with adhesive or adhesive, masking by application of UV or electron beam curable paint, masking with resist material, Examples include masking by physical shielding.

Thus, the decorative sheet for thermoforming of the present invention is obtained. In the vacuum molding simultaneous decorating method, SMC pressure thermoforming, etc., in order to improve the adhesion to the substrate, the cured layer of the resin composition obtained by subjecting a layer made of a general-purpose adhesive or adhesive to the surface treatment You may provide in the surface on the opposite side.
For example, as an adhesive, acrylic resin, urethane resin, urethane-modified polyester resin, polyester resin, unsaturated polyester resin, epoxy resin, epoxy acrylate resin, diallyl phthalate resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin Synthetic rubbers such as vinyl chloride-vinyl acetate copolymer resin, natural rubber, SBR, NBR, and silicone rubber, crystalline polymers, and the like can be used. Solvent type or solventless type can be used.

  The pressure-sensitive adhesive is not particularly limited as long as it has tackiness at the temperature at which it is thermoformed. For example, solvents such as acrylic resin, isobutylene rubber resin, styrene-butadiene rubber resin, isoprene rubber resin, natural rubber resin, silicone resin, etc. Type adhesive, acrylic emulsion resin, styrene butadiene latex resin, natural rubber latex resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, styrene-ethylene-butylene copolymer resin, ethylene-vinyl acetate resin Solvent-free pressure-sensitive adhesives such as polyvinyl alcohol, polyacrylamide, and polyvinyl methyl ether.

  In addition, for the purpose of protecting the curable resin layer during storage or transportation, a cover sheet may be provided on the curable resin layer side and peeled off during or after thermoforming.

(Simultaneous thermoforming decoration)
The decorating sheet for thermoforming of the present invention can be used as a sheet for simultaneous decorating in various thermoforming. Specifically, it can be used for injection molding (insert molding) method, vacuum molding simultaneous decorating method, SMC pressure thermoforming, or the like.

(Injection molding method)
In the method of obtaining the injection molding mold by mounting the thermoforming decorative sheet of the present invention in an injection mold, the injection molding machine, the mounting method, and the like may be performed by known methods. Further, it may be preformed in accordance with a desired mold before injection molding. As a general example, the decorative sheet for thermoforming of the present invention is mounted in a mold so that the cured layer of the surface-treated resin composition becomes a mold surface, and is used for injection molding. The resin is injected and integrated.

  The resin used for injection molding is not particularly limited, and known injection molding resins can be used. Specifically, ABS polymer alloys such as ABS resin, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin, PBT (polybutylene terephthalate) / ABS, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic acid ester / styrene resin, PC resin, PMMA (poly) Methyl methacrylate) resin, PP (polypropylene) resin, and the like.

Various inorganic fillers can be added to the injection resin in order to prevent deformation during or after molding. The inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, silica and the like.
Furthermore, conventional additives may be added as long as the moldability is not inhibited. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, ozonization inhibitors, activators , Antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants and wake accelerators You may mix | blend additives, such as an agent. These additives may be used alone or in combination of two or more. A colorant may also be added.

The injection molding conditions are not particularly limited, and may be injection condition settings and mold temperature settings according to the injection resin. The mold temperature may be controlled by water cooling to about 100 ° C for both cavity side mold and core side mold in polypropylene resin and ABS resin insert molding, but warpage may occur depending on the shape of the transferred material after insert molding. In such a case, mold temperature control may be performed by providing a temperature difference between the cavity side mold and the core side mold. In addition, in order to warm the decorative sheet inserted in the mold to the mold temperature before filling with the injection resin, an injection delay time for holding the decorative sheet in the range of 1 to 100 seconds in the mold clamped may be set. good.
The resin temperature of the injection resin is not particularly limited, but is preferably about 180 to 250 ° C. at which injection is possible as long as it is a thermoplastic resin such as polypropylene resin or ABS resin.

(Vacuum forming simultaneous decoration method)
In the method of sticking and integrating the decorative sheet for thermoforming of the present invention on an adherend by a vacuum forming method, the vacuum forming machine and the vacuum forming method may be performed by known methods. As a general example, the decorative sheet for thermoforming according to the present invention is partially or entirely outer peripheral so that the cured layer of the surface-treated resin composition is on the surface opposite to the adherend. Is fixed with a clamp or the like, heated under an vacuum by an infrared irradiation device or the like to plasticize the sheet, and then attached to an adherend and integrated. Heating conditions, vacuum conditions, and the like can be appropriately selected depending on the adherend to be used and the base material of the decorative sheet.

  The adherend used in the present invention is not particularly limited and may be anything as long as it is transparent or opaque and requires surface design. Specifically, various shapes such as resin, metal, glass, wood, and paper can be used, and the shapes may be decorated by a regular decoration method such as painting, plating, and scratching.

For example, the resin may be the same as the resin for injection molding. Further, two or more kinds of the exemplified resins may be mixed or multilayered. Furthermore, reinforcing additives such as inorganic fillers, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, and other conventional additives may be added, and these additives are used alone. Or you may use 2 or more types together.

(SMC pressure thermoforming)
In the method of superposing the decorative sheet for thermoforming of the present invention so as to be in contact with SMC and pressurizing and thermoforming, the pressurizing thermoforming machine and pressurizing thermoforming method may be performed by known methods. When showing a general example, the surface side opposite to the cured product layer of the surface-treated resin composition of the decorative sheet for thermoforming of the present invention (the adhesive layer side when there is an adhesive layer) is SMC. A decorative molded product can be obtained by pressurizing and thermoforming the layers so as to be in contact with each other. Specifically, by placing the decorative sheet for thermoforming of the present invention inside the mold so that the decorative surface is in contact with the inside of the mold, and then placing the SMC on top of each other, pressurizing and hot press molding A SMC decorative molded product can be obtained. The mold shape, pressure, heating temperature, time, etc. are not particularly limited, and decoration can be performed within the range of normal SMC molding.

  The SMC used in the present invention is not particularly limited, and a known one may be used. For example, radical curable resins such as unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, vinyl acetate, styrene, styrene-substituted products, methyl (meth) acrylate, (meth) Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid A radical polymerizable monomer such as glycidyl, (meth) acrylonitrile, (meth) acrylamide, maleic anhydride, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, phenylmaleimide, a radical polymerization initiator, and optionally a low shrinkage agent, Curing catalyst, filler, internal separation A resin mixture kneaded with an agent, thickener, colorant, etc., impregnated into a fibrous reinforcing material in a sheet form and thickened, or the resin composition is made of glass fiber, amide, aramid, vinylon, polyester Further, those kneaded with organic fibers such as phenol, carbon fibers, metal fibers, ceramic fibers and natural fibers can be used. In particular, SMC using styrene as a monomer is preferable.

  Since the decorative sheet for thermoforming of the present invention contains a polysiloxane bond as a cured product layer, it is presumed that the polysiloxane further undergoes thermal condensation during pressure thermoforming. Accordingly, a molded product that is superior in surface hardness can be obtained.

  Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “parts” and “%” are weight standards.

(Synthesis Example 1 [Synthesis Example of Polysiloxane])
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet is charged with 415 parts of methyltrimethoxysilane (MTMS) and 756 parts of 3-methacryloyloxypropyltrimethoxysilane (MPTS). The temperature was raised to 60 ° C. with stirring under aeration of gas. Next, a mixture consisting of 0.1 part of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product.
By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. 1000 parts of polysiloxane (a1-1) which is 0.0% was obtained.
The "active ingredient" is a value obtained by dividing the theoretical yield (parts by weight) when all the methoxy groups of the silane monomer used undergo hydrolysis condensation reaction by the actual yield (parts by weight) after hydrolysis condensation reaction, That is, it is calculated by the formula [theoretical yield when all methoxy groups of the silane monomer undergo hydrolysis condensation reaction (parts by weight) / actual yield after hydrolysis condensation reaction (parts by weight)].

(Synthesis Example 2 [Synthesis Example of Composite Resin (A)])
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate were charged under a nitrogen gas flow. The temperature was raised to 80 ° C. while stirring. Next, 62.1 parts of styrene monomer, 15 parts of butyl acrylate (BA), 40.5 parts of methyl methacrylate (MMA), 27.9 parts of 2-hydroxyethyl methacrylate (HEMA), 4.5 parts of MPTS, n-butyl acetate A mixture containing 15 parts of 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) was dropped into the reaction vessel over 4 hours at the same temperature while stirring under a stream of nitrogen gas. . After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “A-3” and 12.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was kept at the same temperature for 4 hours. By stirring, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Next, by stirring at the same temperature for 10 hours, a reaction product having a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 162.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 was added to the reaction product, and the mixture was stirred for 5 minutes. Then, 27.5 parts of deionized water was added at 80 ° C. Stirring was carried out for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -27.3 parts of butyl were added to obtain 600 parts of a composite resin (A-1) composed of a polysiloxane segment and a vinyl polymer segment having a nonvolatile content of 50.0%.

(Synthesis Example 3 (same as above))
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate were charged under a nitrogen gas flow. The temperature was raised to 80 ° C. while stirring. Next, 15 parts of methyl methacrylate (MMA), 45 parts of n-butyl methacrylate (BMA), 39 parts of 2-ethylhexyl methacrylate (EHMA), 1.5 parts of acrylic acid (AA), 4.5 parts of MPTS, 2-hydroxyethyl A mixture containing 45 parts of methacrylate (HEMA), 15 parts of n-butyl acetate and 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) was stirred at the same temperature under a stream of nitrogen gas. And dropped into the reaction vessel in 4 hours. After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “A-3” and 12.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was kept at the same temperature for 4 hours. By stirring, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Next, by stirring at the same temperature for 10 hours, a reaction product having a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 162.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 was added to the reaction product, and the mixture was stirred for 5 minutes. Then, 27.5 parts of deionized water was added at 80 ° C. Stirring was carried out for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -27.3 parts of butyl were added to obtain 600 parts of a composite resin (A-2) composed of a polysiloxane segment and a vinyl polymer segment having a nonvolatile content of 50.0%.

(Formulation Examples 1-4 and Comparative Formulation Examples 1-3)
Based on the formulation shown in Table 1, clear paints (paint-1) to (paint-4) and comparative clear paints (specific paint-1) to (specific paint-3) were prepared.

A802: Acrydic A802 [acrylic resin made by DIC Corporation].
C7-164: Unidic C7-164 [ultraviolet curable resin, manufactured by DIC Corporation].
D-110N: Takenate D-110N [manufactured by Mitsui Chemicals Polyurethane Co., Ltd.].
PETA: Pentaerythritol triacrylate.
I-184: Irgacure 184 [manufactured by Ciba Japan Co., Ltd., a photopolymerization initiator].
Ti-400: Tinuvin 400 [hydroxyphenyltriazine-based ultraviolet absorber Ciba Japan Co., Ltd.].
Ti-123: Tinuvin 123 [hindered amine light stabilizer (HALS) manufactured by Ciba Japan Ltd.].

(Examples 1 to 4 and Comparative Examples 1 to 3 Manufacturing method of thermoforming decorative sheet)
(Formation and curing of resin composition layer)
The clear paints (coating-1) to (coating-4) and the comparative clear paints (comparing coating-1) to (comparing-3) prepared based on the formulation examples shown in Table 1 were soft shine X1130. A film having a resin composition layer was obtained by coating on a biaxially stretched PET film manufactured by Toyobo Co., Ltd. with a bar coater such that the dry film thickness was 20 μm. A specific configuration is shown in Table 2.

The film having the resin composition layer was cured by both UV curing and thermal curing, or by UV curing or thermal curing. The curing method for each film is shown in Table 2.
(UV curing)
The film having the resin composition layer was dried at 80 ° C. for 4 minutes, and then irradiated with ultraviolet rays at a dose of about 1000 mJ under a mercury lamp with a lamp output of 1 kW to cure the resin composition layer.
(Thermosetting)
The film having the resin composition layer was allowed to stand at 40 ° C. for 3 days to cure the resin composition layer.

(Formation and curing of adhesive layer)
50 parts of bisphenol A type epoxy acrylate “Dicklight UE8300” (number average molecular weight of about 2000, hydroxyl value of about 230 mg KOH / g) manufactured by DIC Corporation, hexamethylene diisocyanate polyisocyanate “Bernock DN−” manufactured by DIC Corporation 981 "(nonvolatile content = 75%, NCO% = about 14%), 50 parts aluminum hydroxide“ B1403 ”manufactured by Nippon Light Metal Co., Ltd. as filler, and Nippon Oil & Fats Co., Ltd. as radical polymerization initiator The composition for adhesive layer was prepared by stirring 0.5 parts of perbutyl I and 40 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) as an organic solvent using a homodisper.

  On the surface of the film having the resin composition layer opposite to the resin composition layer, the adhesive layer composition was applied with a bar coater so that the film thickness after drying was 25 μm, at 80 ° C. Dry for 3 minutes. After drying, the adhesive layer was cured by aging at 50 ° C. for 2 days.

(Gas treatment)
Next, the obtained film having the resin composition layer is inserted and fixed in a stainless steel treatment container for contacting sulfur trioxide containing gas having an internal volume of 300 L heated to 45 ° C., and the lid of the container is attached. It was closed and contacted with the sulfur trioxide-containing gas under the conditions of a gas concentration of 1.2 vol%, a time of 2.5 minutes, and a dilution gas dew point of −60 ° C. Subsequently, it was washed with ion exchanged water at 50 ° C. for 5 minutes and 24 hours to obtain a decorative sheet for thermoforming.

(Example 5: Production method of decorative sheet for thermoforming)
On the PET film, a gravure printing ink “XS-756” manufactured by DIC Corporation was used to print a pattern having a thickness of 3 μm using a gravure printing machine to obtain a film having a printed layer. Then, the said clear coating material (coating-2) was apply | coated with the bar coater so that the dry film thickness might be set to 20 micrometers on the printing layer of a film, and the resin composition layer was formed.

(Ink used)
DIC Corporation gravure printing ink "XS-756" Red DIC Corporation gravure printing ink "XS-756" Blue DIC Corporation gravure printing ink "XS-756" yellow

  Next, in the same manner as in Example 1, curing of the cured resin layer, formation and curing of the adhesive layer, and gas treatment were performed to obtain a decorative sheet for thermoforming. A specific configuration is shown in Table 3.

(Examples 6-8 Manufacturing method of thermoforming decorative sheet)
A decorative layer and a resin composition layer were formed in the same manner as in Example 5, and gas treatment was performed without forming an adhesive layer to obtain a decorative sheet for thermoforming. A specific configuration is shown in Table 3.

(SMC pressure thermoforming method)
The obtained decorative sheet for thermoforming is cut into a size of 20 cm × 20 cm, and is used for the SMC at the center of the lower mold (female mold, the surface of the molded product) using a 100 t press machine of Yamamoto Iron Works Co., Ltd. Place the resin composition layer side of the integrally molded decorative sheet facing down, then stack SMC, mold temperature upper mold 130 ° C, lower mold 145 ° C, molding pressure 10 MPa, pressurization time 6 minutes The SMC decorative molded product of 30 cm × 30 cm × 3.5 mm was obtained. As SMC, SMC “Dickmat 2622” manufactured by DIC Kako Co., Ltd. was used.

(Vacuum forming simultaneous decoration method)
After clamping the periphery with the resin composition layer side of the obtained decorative sheet for thermoforming up, the upper and lower boxes of “NGF-0709 molding machine” manufactured by Fuse Vacuum Co., Ltd. are closed, and the inside of the box is almost completely vacuumed After that, a middle infrared heater manufactured by Helius was used as the heater, and indirect heating was performed from the upper surface of the obtained sheet. After heating the surface of the resin composition layer to 185 ° C., the table on which a smooth stainless steel plate (100 mm × 100 mm × 2 mm thickness) is placed is lifted, 0.2 MPa of compressed air is blown into the upper box, and the obtained sheet PET The base material side was pressed against the stainless steel plate to obtain a vacuum formed product.

(Injection molding (insert molding) method)
The obtained decorative sheet for thermoforming was adhered so that the surface of the resin composition layer was in contact with the female mold of the injection mold, and heated at a mold temperature of 50 ° C., and then injected resin (manufactured by Teijin Kasei Co., Ltd.). Multilon T-3714) was heated to 270 ° C., injected into a mold and integrally molded to obtain an injection molded product. The injection molding machine used was EC75N-1.5Y manufactured by Toshiba Machine Co., Ltd. As the injection mold, a tray-shaped mold having a size of 100 (L) × 100 (W) × 12.5 (H) mm, corner R = 10 mm, rising portion R = 5R, draft angle 18.5 ° was used. .

<Physical property evaluation method>
(Number of cracks)
The number of cracks generated per 100 cm ² of the resin composition layer surface of the decorative molded product obtained by the molding was counted. The thing which generate | occur | produced in large quantities and cannot be counted was set as "x".

(Anti-fouling, oil-resistant dirt)
0.2 ml of pseudo oil stains (a mixture of olive oil, oleic acid, and oil red) was dropped onto the surface of the resin composition layer of the decorative molded product obtained by the molding. After leaving it for 60 seconds, it was poured vertically into water at 35 to 38 ° C., and the time until the pseudo oil stain was lifted was measured. The oil stain resistance is improved as the oil stain rises in a short time. If the oil stain did not rise even after waiting 10 minutes, “x” was assigned.

  Examples 1 to 6 were performed by the SMC pressure thermoforming method, Example 7 was performed by the vacuum molding simultaneous decorating method, and Example 8 was performed by the injection molding (insert molding) method to obtain a decorative molded product. The results are shown in Tables 2-4.

As a result, the SMC decorative molded products of Examples 1 and 2 were both free from molding cracks and excellent in the rising speed of oil stains. The SMC decorative molded product of Example 3 is an example in which the polysiloxane bond and the benzene ring are slightly less, but the lifting speed of the oil stain is somewhat slow. The SMC decorative molded product of Example 4 is an example in which a siloxane resin having no benzene ring and an acrylic styrene resin are mixed, but several streak cracks were generated on the surface.
The SMC decorative molded products of Examples 5 to 6 are examples in which a decorative layer is provided, but even if the decorative layer is provided, there was no effect on the number of cracks generated or the rising speed of oil stains.
Example 7 was a vacuum molded product, and Example 8 was an injection molded product. In all cases, there was no generation of molding cracks, and the oil dirt was lifted quickly.
The SMC decorative molded product of Comparative Example 1 is an example having a polysiloxane bond but not having a benzene ring, and the lifting speed of oil stains was very slow. The SMC decorative molded product of Comparative Example 2 is an example in which only an acrylic styrene resin is used, but a large number of cracks have occurred after molding. The SMC decorative molded product of Comparative Example 3 is an example in which a UV curable resin having a benzene ring is used, and since it does not have a polysiloxane bond, the rising speed of the oil stain of the molded product has been slow.

Claims (8)

A polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, provided on the base sheet; The cured product of the resin composition containing the composite resin (A) in which the vinyl polymer segment (a2) is bonded by the bond represented by the general formula (3) is surface-treated with a sulfur trioxide-containing gas. A decorative sheet for thermoforming, characterized by comprising:

(1)

(2)
(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (where R ⁴ is A single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or an aralkyl having 7 to 12 carbon atoms. Represents a group.)

(3)
(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do) The decorative sheet for thermoforming according to claim 1, wherein at least one of R ¹ , R ² and R ^{3 in} the general formulas (1) and (2) is the aryl group. The decorative sheet for thermoforming according to claim 1 or 2, wherein at least one of R ¹ , R ² and R ^{3 in} the general formulas (1) and (2) is a group having the polymerizable double bond. The decorative sheet for thermoforming according to any one of claims 1 to 3, wherein the vinyl polymer segment (a2) has an alcoholic hydroxyl group, and the resin composition contains a polyisocyanate (B). The said base material sheet is a thermoplastic resin sheet, The decorating sheet for thermoforming in any one of Claims 1-4. A decorative molded product obtained by superimposing the thermoforming decorative sheet according to any one of claims 1 to 5 so as to be in contact with a sheet molding compound and performing pressure thermoforming. A decorative molded product obtained by mounting the decorative sheet for thermoforming according to any one of claims 1 to 5 in an injection mold and performing injection molding. A decorative molded product obtained by attaching the decorative sheet for thermoforming according to any one of claims 1 to 5 to an adherend by a vacuum forming method.