JP2006249323A - Photosetting resin composition, photosetting sheet and method for producing molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting resin composition capable of providing a photosetting sheet having good design property, excellent in abrasion resistance, weather resistance and chemical resistance, having good adhesion between a layer of the photosetting resin composition and a substrate sheet and good appearance of the surface, free from surface tackiness and excellent in processability and storage stability and a photosetting sheet using the composition and to provide a method for producing a molded article by using the sheet. <P>SOLUTION: The photosetting resin composition comprises (a-1) a thermoplastic resin having a photopolymerizable functional group, (a-2) a photopolymerization initiator and (a-3) inorganic fine particles. The photosetting resin composition is obtained by previously carrying out hydrolytic condensation reaction of a monomer of a radically polymerizable silane compound (s-1) or its hydrolyzate with a monomer of non-radically polymerizable silane compound (s-2) or its hydrolyzate in the presence of the inorganic fine particles (a-3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photocurable resin composition, a photocurable sheet using the composition, and a method for producing a molded article using the sheet. The present invention is particularly photocuring that has excellent appearance, design, abrasion resistance, chemical resistance and weather resistance, has excellent storage stability, and can provide a photocurable sheet having no surface tackiness. The present invention relates to a curable resin composition, a photocurable sheet using the composition, and a method for producing a molded article using the sheet.

  As a method of decorating the surface of a plastic product at the same time as molding, (1) a method of pre-patterning the inner surface of the mold, (2) mounting a transfer film on the inner wall surface of the mold, A method of transferring a pattern or the like to the outer surface of a molded product, and (3) a method of pasting a functional sheet or printed sheet on the inner wall surface of a mold and pasting the sheet on the surface of the molded product simultaneously with molding are proposed. ing. With respect to the method (2) or (3), for example, after forming a weather resistance imparting sheet or printed sheet on the inner wall surface of the mold, a molded product whose surface is coated with the sheet by injection molding a molding resin Has been proposed (see, for example, Patent Documents 1, 2, and 3).

  Not only these molded products but also molded products by general methods are exposed to various damage factors in the molding process and in the actual usage environment of the molded products. In order to maintain the beauty of these molded products over a long period of time, surface scratch resistance (abrasion resistance, surface hardness, etc.) is an important characteristic to be provided.

  However, in the above technique, the surface hardness of the obtained molded product is insufficient because the decoration and the functional addition are performed by transfer of a thermoplastic sheet or printing. For example, when weather resistance is imparted to a molded article, a high weather resistance sheet made of polyvinylidene fluoride (PVDF) or the like may be used, but there is a problem that sufficient surface hardness cannot be obtained.

  On the other hand, in order to obtain a molded product having a high surface hardness, a sheet having a high surface hardness that has been previously cross-linked must be used. However, such a sheet is difficult to apply to a three-dimensional molded product.

  A photocurable sheet was proposed in which a photocurable resin layer formed of a resin composition containing an acrylic resin, a compound having a reactive vinyl group, and a photopolymerization initiator and a sheet substrate are laminated (for example, , See Patent Document 4). However, in this sheet, since the sheet before photocuring contains a compound having a low molecular weight reactive vinyl group, there is a phenomenon that the surface has adhesiveness or the surface adhesiveness changes with time. Occurs and the storage stability in the roll state is poor. Specifically, there are problems such as sticking and unwinding, and exudation of compounds from both ends unless stored at low temperatures. Furthermore, due to its surface tackiness, there is a problem that it cannot adhere to the mold surface and cannot be removed when it is molded continuously for a long time, or sticks to the transport roll in the printing process when used as a printing sheet. It was happening.

  On the other hand, by laminating a composition containing a resin having an alicyclic epoxy group or radical polymerizable unsaturated group in the side chain, inorganic fine particles, and a photopolymerization initiator on a base sheet, it can be used for in-mold molding or insert molding. The representative method (3) is applicable, and can be advantageously used for the production of molded articles with good design properties. It has excellent wear resistance, weather resistance and chemical resistance, and is tacky. There is disclosed a photocurable sheet having a photocurable resin composition layer excellent in processability and storage stability on the surface (for example, see Patent Document 5).

  The above-mentioned photocurable resin composition or photocurable sheet has both excellent moldability before photocuring and excellent surface properties (hardness, scratch resistance, weather resistance, adhesion, etc.) after photocuring. It is suitably used for automotive interior / exterior materials such as center pillars, side moldings, door moldings, and console boxes. However, for example, in exterior applications where the degree of exposure to direct sunlight, such as the upper surface of a sunroof or rear spoiler, is extremely high, the photocurable resin composition layer is discolored, cracked, or a base sheet. There was a case where the problem of more peeling occurred.

  In addition, the above-mentioned photocurable resin composition or photocurable sheet is excellent in storage stability, but it is used for a long time in an environment where the temperature is extremely high, such as in an outdoor warehouse under a hot sun in a tropical / subtropical region. In some cases, the curing reaction of the photocurable resin composition proceeds partially, causing problems such as gelation of the photocurable resin composition and reduced elongation of the photocurable sheet. It was.

  On the other hand, Patent Documents 6 to 10 describe coating compositions containing an alkoxysilane compound such as a polyfunctional (meth) acrylate compound, colloidal silica, and (meth) acrylsilane. Although these coating compositions exhibit relatively good abrasion resistance, transparency and chemical resistance after curing, they have weather resistance and adhesion to a substrate sheet, especially after a long-term weather resistance test. Adhesion was not sufficient. In addition, the coating composition before curing has surface tackiness, and a sheet obtained by laminating a layer of these coating compositions on a base sheet is storage stability and moldability (insert / in-mold molding). The printability was extremely inferior.

JP-A-60-250925 Japanese Patent Publication No.59-36841 Japanese Patent Publication No. 8-2550 Japanese Patent Publication No.7-323 JP 2002-80550 A JP-A-8-209028 JP-A-9-194760 JP-A-57-13214 Japanese Unexamined Patent Publication No. 7-258582 Japanese Patent Laid-Open No. 2003-213067

  The present invention has been made on the basis of the above-mentioned background. The object of the present invention is good design, excellent wear resistance, weather resistance and chemical resistance, and a photocurable resin composition. A photocurable resin composition capable of providing a photocurable sheet having good adhesion between the layer and the base sheet and the surface appearance, no surface tackiness, and excellent workability and storage stability, It is providing the photocurable sheet | seat using this composition, and the manufacturing method of the excellent molded article using this sheet | seat.

  That is, the present invention is a photocurable resin composition containing a thermoplastic resin (a-1) having a photopolymerizable functional group, a photopolymerization initiator (a-2), and inorganic fine particles (a-3). In the presence of the inorganic fine particles (a-3), the monomer or hydrolyzate of the radically polymerizable silane compound (s-1) and the non-radically polymerizable silane compound (s-2) are previously added in the presence of the inorganic fine particles (a-3). Provided is a photocurable resin composition (that is, a photocurable resin composition (A)) obtained by subjecting a monomer or a hydrolyzate to a hydrolytic condensation reaction.

  Moreover, this invention provides the photocurable sheet which has a layer of the said photocurable resin composition (A) on a base material sheet (B).

  Furthermore, this invention provides the photocurable decorating sheet which formed at least 1 layer chosen from the printing layer, the vapor deposition layer, the contact bonding layer, and the primer layer in the base material sheet (B) side of the said photocurable sheet. .

  Furthermore, this invention provides the molded product using the said photocurable sheet and the photocurable decorating sheet, and the manufacturing method of the molded product.

  According to the present invention, the design property is good, the wear resistance, the weather resistance and the chemical resistance are excellent, and the adhesion between the layer of the photocurable resin composition and the base sheet and the appearance of the surface are good. A photo-curable resin composition that is capable of providing a photo-curable sheet having no surface tackiness, excellent processability and storage stability, and excellent appearance, designability, and abrasion resistance using this composition. A photocurable sheet capable of giving a molded product exhibiting properties, weather resistance and chemical resistance, and capable of exhibiting processability, storage stability, appearance, sheet handling property, and the like, and this sheet A molded article having excellent characteristics is provided.

  The preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments, and it goes without saying that various modifications can be made within the scope of the spirit and idea thereof. It is.

  The photocurable resin composition of the present invention contains a thermoplastic resin (a-1) having a photopolymerizable functional group, a photopolymerization initiator (a-2), and inorganic fine particles (a-3), and is inorganic. In the presence of the fine particles (a-3), a monomer or hydrolyzate of the radical polymerizable silane compound (s-1) and a monomer of the non-radically polymerizable silane compound (s-2) or It is a product obtained by subjecting a hydrolyzate to a hydrolytic condensation reaction.

  The thermoplastic resin (a-1) having a photopolymerizable functional group has two or more photopolymerizable functional groups in one molecule and is cured by a photopolymerization reaction to form a crosslinked product. A plastic resin is preferred. As a photopolymerizable functional group of such a compound, a functional group having an ethylenically unsaturated group such as a vinyl group or a (meth) acryl group and reacting by a photoradical polymerization mechanism, or a photocation such as an alicyclic epoxy group. Examples thereof include functional groups that react by a polymerization mechanism.

  From the viewpoint of the weather resistance of the thermoplastic resin (a-1), the thermoplastic resin (a-1) is preferably an acrylic resin having a photopolymerizable functional group in the molecule.

  Furthermore, from the viewpoint of good wear resistance and chemical resistance, the thermoplastic resin (a-1) is more preferably an acrylic resin having a photopolymerizable functional group in the side chain.

  In particular, the photocurable resin composition (A) contains a thermoplastic resin (a-1) having a photopolymerizable functional group in the side chain, and substantially contains a crosslinkable compound other than (a-1). In the case of a structure having no, it is preferable because a photocurable sheet having both extremely good wear resistance, moldability, and storage stability can be obtained. By introducing a structure having a photopolymerizable functional group in the side chain in this way, the cross-linking reaction proceeds between the side chains, so that even if a low molecular weight crosslinkable compound is not contained, good wear resistance is achieved. In addition to being expressed, the absence of a low molecular weight crosslinkable compound provides the advantage that the sheet surface is not sticky and has excellent storage stability.

  This photopolymerizable functional group is a polymer that proceeds by irradiation with active energy rays. As a preferable example, a radical polymerizable unsaturated group or an alicyclic epoxy group represented by the following structural formula (1) is used. Can be mentioned.

  As a thermoplastic resin which has a radically polymerizable unsaturated group in a side chain, what has a radically polymerizable unsaturated group in a polymer side chain whose glass transition temperature is 25-175 degreeC is mentioned, for example. More preferably, the glass transition temperature has a lower limit of 30 ° C. or higher and an upper limit of 150 ° C. or lower.

  Specifically, a polymer obtained by polymerizing or copolymerizing the following compounds (1) to (8) as a polymer and introducing a radically polymerizable unsaturated group by the methods (a) to (d) described later. Can be used.

(1) Monomers having a hydroxyl group: N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (2) Monomers having a carboxyl group: (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc. (3) Monomers having an epoxy group: glycidyl (meth) acrylate, 3,4- (4) Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc. (5) Monomers having an amino group: (Meth) acrylamide, diacetone acrylamide, di Methylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. (6) Monomer having sulfone group: 2-acrylamido-2-methylpropanesulfonic acid, etc. (7) Monomer having isocyanate group: 2, Adducts of radically polymerizable monomers having diisocyanate and active hydrogen, such as equimolar adducts of 4-toluene diisocyanate and 2-hydroxyethyl acrylate, 2-isocyanate ethyl (meth) acrylate, etc. (8) Further, In order to adjust the glass transition temperature of the copolymer or to match the physical properties of the photocurable sheet, the above compound can be copolymerized with a monomer copolymerizable therewith. Examples of such copolymerizable monomers include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N-phenylmaleimide, and cyclohexylmaleimide. And imide derivatives such as N-butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene.

  Next, radically polymerizable unsaturated groups are introduced into the polymer obtained as described above by the methods (i) to (d) described below.

(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.
(B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the aforementioned monomer having a hydroxyl group is subjected to a condensation reaction.
(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the aforementioned monomer having a hydroxyl group or monomer having a carboxyl group is subjected to an addition reaction.
(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group, a monomer having an aziridinyl group, a monomer having an isocyanate group, or An equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer is subjected to an addition reaction.

  The above reaction is preferably carried out while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air.

  Examples of the thermoplastic resin having an alicyclic epoxy group in the side chain used in the present invention include those having an alicyclic epoxy group in the polymer side chain having a glass transition temperature of 25 to 175 ° C. . More preferably, the glass transition temperature has a lower limit of 30 ° C. or higher and an upper limit of 150 ° C. or lower. When a specific synthesis example is given, for example, as a first method, a (meth) acrylate (9) having an alicyclic epoxy group is subjected to a known polymerization method such as a solution polymerization method in the presence of a radical polymerization initiator. It can be obtained by homopolymerization or copolymerization with other copolymerizable monomers as shown in the above (1) to (8).

  Moreover, the thermoplastic resin which has an alicyclic epoxy group in a side chain can be obtained also by methods other than the said homopolymerization or copolymerization. For example, as a second method, a compound having an alicyclic epoxy group and a first reactive group is reacted with a thermoplastic resin having a second reactive group that reacts with the first reactive group. Can be obtained. Typical examples of the combination of the first reactive group and the second reactive group include combinations of isocyanate groups and hydroxyl groups as shown in Table 1 below.

  In the first method, the (meth) acrylate (9) having an alicyclic epoxy group is not particularly limited as long as it can be copolymerized with other radical polymerizable monomers. Is a compound represented by the following structural formula (2).

(In the above formula, R represents a methyl group or a hydrogen atom, and n is an integer of 0 to 5)

  The amount of the photopolymerizable functional group in the side chain of the thermoplastic resin (a-1) is double bond equivalent (average molecular weight per one side chain radical polymerizable unsaturated group) or alicyclic epoxy equivalent (side chain). The average molecular weight per alicyclic epoxy group) is preferably 3000 g / mol or less on average from the charged value, from the viewpoint of improving scratch resistance and wear resistance. A more preferable range is an average of 1200 g / mol or less, and a most preferable range is an average of 800 g / mol or less.

  In this way, by introducing a plurality of photopolymerizable functional groups involved in crosslinking into the thermoplastic resin, there is no need to use a low molecular weight crosslinking compound, and even during long-term storage and thermoforming, the surface It becomes possible to improve hardened | cured material property efficiently, without having adhesiveness.

  The thermoplastic resin (a-1) has good mold releasability when insert molding or in-mold molding of a photocurable sheet formed using the photocurable resin composition (A), From the viewpoint of the surface hardness of the insert / in-mold product after photocuring, the number average molecular weight is preferably 5,000 or more. On the other hand, the number average molecular weight is preferably 2,500,000 or less from the viewpoint of ease of synthesis and appearance, and from the viewpoint of adhesion with the base sheet (B). More preferably, the lower limit is 10,000 or more and the upper limit is 1,000,000 or less.

  Moreover, it is preferable that the glass transition temperature of the thermoplastic resin (a-1) is adjusted to 25 to 175 ° C. The lower limit of the glass transition temperature is more preferably 30 ° C. or higher, and the upper limit is more preferably 150 ° C. or lower. From the viewpoint of mold releasability of the photocurable sheet during insert molding or in-mold molding and the surface hardness of the insert / in-mold molded product after photocuring, the glass transition temperature is preferably 25 ° C. or higher. On the other hand, it is preferable that a glass transition temperature is 175 degrees C or less from a viewpoint of the handleability of a photocurable sheet.

  In consideration of the glass transition temperature of the thermoplastic resin obtained, it is preferable to use a vinyl polymerizable monomer that has a high glass transition temperature as a homopolymer.

  Furthermore, from the viewpoint of improving the weather resistance of the thermoplastic resin, it is preferable to use (meth) acrylates as the main component as the vinyl polymerizable monomer.

  Further, when adding the inorganic fine particles (a-3) to the photocurable resin composition (A) used in the present invention, as described later, the functional groups (hydroxyl groups, A vinyl polymerizable group having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated silyl group and an alkoxysilyl group in the molecule. Since the monomer works to further improve the physical properties such as rigidity, toughness and heat resistance of the resulting photocurable resin composition, a part of the vinyl polymerizable monomer component in which such a functional group can be radically polymerized. It may be contained as.

  Examples of vinyl polymerizable monomers containing such reactive groups in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, Examples include vinyltrimethoxysilane and γ- (meth) acryloyloxypropyltrimethoxysilane.

  The photocurable resin composition (A) may contain a photopolymerization initiator (a-2). Examples of the photopolymerization initiator (a-2) include a photoradical polymerization initiator that generates radicals upon irradiation with active energy rays and a photocationic polymerization initiator that generates an acid. Of the thermoplastic resin (a-1), When the photopolymerizable functional group is a radically polymerizable unsaturated group, a photoradical polymerization initiator is used, and when it is an alicyclic epoxy group, a photocationic polymerization initiator is used.

  As the radical photopolymerization initiator, a known compound can be used and is not particularly limited. However, in consideration of yellowing during curing and deterioration during weathering, such as acetophenone, benzophenone, and acylphosphine oxide It is preferable to use an initiator that does not contain an amino group in the molecule. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide and the like are preferable. Of these, care must be taken because some molding methods temporarily have temperatures above the boiling point of the compound. In order to increase the surface hardness of the molded product, an additive such as n-methyldiethanolamine that suppresses polymerization hardening inhibition by oxygen may be added. In addition to these photopolymerization initiators, various peroxides may be added in consideration of curing using heat during molding. When the photocurable sheet contains a peroxide, it must be cured at 150 ° C. for about 30 seconds. Therefore, a peroxide having a low critical temperature, such as lauroyl peroxide, t-butylperoxy-2, etc. -Ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.

  The addition amount of the radical photopolymerization initiator is desirably 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (a-1), since the residual amount after curing affects the weather resistance, and particularly the radical photopolymerization initiator. However, when it is an amino-type radical photopolymerization initiator, 1 mass part or less is preferable.

  As the photocationic polymerization initiator, known compounds can be used, and are not particularly limited, and examples thereof include diaryliodonium salts, triarylsulfonium salts, iron arene (aromatic hydrocarbon) complexes, and the like. Among these, a triarylsulfonium salt represented by the following structural formula (3) is more preferable in consideration of reactivity with a compound having an alicyclic epoxy group, coloring problems, and the like.

(In the above formula, R ¹ represents a substituted or unsubstituted aromatic ring via a carbon-carbon bond or a carbon-sulfur bond, and R ² and R ³ each represent a substituted or unsubstituted aromatic ring)

  As for the addition amount of a photocationic polymerization initiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of thermoplastic resins (a-1).

  Inorganic fine particles (a-3) are added to the photocurable resin composition (A) for the purpose of further improving scratch resistance and abrasion resistance. In the inorganic fine particles (a-3), the type, particle diameter, and form are not particularly limited as long as the obtained photocurable resin composition becomes transparent. Examples of inorganic fine particles include colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), cadmium oxide, antimony oxide, etc. Can be mentioned. These may be used alone or in combination of two or more. Of these, colloidal silica is particularly preferable from the viewpoints of availability, price, transparency of the resulting photocurable resin composition layer, and expression of wear resistance. Here, colloidal silica is obtained by dispersing ultrafine particles of silicic acid anhydride in a suitable liquid medium.

  Colloidal silica can be used in the form of a normal aqueous dispersion or in a form dispersed in an organic solvent. In order to disperse uniformly and stably with the thermoplastic resin (a-1), an organic solvent is used. It is preferable to use colloidal silica dispersed in.

  Examples of such organic solvents include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like. In order to uniformly disperse together with the thermoplastic resin, it is preferable to select an organic solvent capable of dissolving the thermoplastic resin. However, when the photocurable sheet of the present invention is produced, these organic solvents are described later. In order to volatilize by drying by heating, the resin component (b), which is the main component of the base sheet (B), has a boiling point of 80 ° C. or more higher than the glass transition temperature and remains in the photocurable sheet. It tends to remain in the photocurable sheet even if it is 30 ° C. or higher.

  Examples of colloidal silica dispersed in an organic solvent include methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG-ST, xylene / butanol silica sol XBA-ST. , Ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST Commercially available products such as those manufactured by KK) can be used.

  The particle diameter of the inorganic fine particles (a-3) is usually preferably 200 nm or less from the viewpoint of the transparency of the resulting photocurable resin composition layer. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less. Moreover, the addition amount of inorganic fine particles (a-3) is preferably in the range of 5 to 400 parts by mass in terms of solids of inorganic fine particles with respect to 100 parts by mass of solids of the thermoplastic resin (a-1). The lower limit of the addition amount is more preferably 10 parts by mass or more. Further, the upper limit of the addition amount is more preferably 200 parts by mass or less. When the addition amount of the inorganic fine particles is less than 5 parts by mass, the effect of improving the abrasion resistance may not be recognized. When the addition amount exceeds 400 parts by mass, the photocurable resin composition ( Not only the storage stability of A) is lowered, but also the moldability of the resulting photocurable sheet may be lowered.

  In the presence of the inorganic fine particles (a-3) used in the present invention, the radically polymerizable silane compound (s-1) monomer or hydrolyzate and the non-radically polymerizable silane compound (s-2) ) Monomer or hydrolyzate.

  Thus, the surface of the inorganic fine particles (a-3) is treated with silane by hydrolytic condensation reaction of the silane compounds (s-1) and (s-2) in the presence of the inorganic fine particles (a-3). Modification with a hydrolytic condensate of the compound improves compatibility with other components such as the thermoplastic resin (a-1), and dramatically improves the storage stability of the photocurable resin composition (A). be able to. Moreover, various physical properties, such as abrasion resistance, a weather resistance, adhesiveness, storage stability, and chemical resistance, of the obtained photocurable sheet | seat become favorable.

  The radical-polymerizable silane compound (s-1) used in the present invention is a silane compound having at least one radical-polymerizable group in the molecule, and is irradiated with an active energy ray such as ultraviolet rays to cause the thermoplastic resin (a- 1) and inorganic fine particles (a-3) are bonded to each other, contributing to the expression of the surface hardness and wear resistance of the cured photocurable resin composition (A), and the inorganic fine particles (a- 3) It contributes also to hydrophobizing the surface and expressing adhesiveness with a base material sheet (B).

  In this specification, “radical polymerizability” means that radical polymerization can be easily performed by heating or irradiation with active energy rays using an appropriate radical polymerization initiator. The “active energy rays” mean electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, γ rays, and electron beams.

  Examples of the radical polymerizable group in the silane compound (s-1) include radical polymerizable groups such as a (meth) acryl group, an allyl group, a vinyl group, and a styryl group. From the viewpoint of photocuring reactivity, A (meth) acryl group is preferred.

The silane compound having a (meth) acryl group is represented by the following structural formula (4), for example.
CH ₂ = C (R ² ) COO (CH ₂ ) _p SiR ³ _n (OR ¹ ) _3-n (4)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, R ² represents a hydrogen atom or a methyl group, R ³ represents an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino group. A hydrocarbon residue having 1 to 10 carbon atoms which may have a bond, n is an integer of 0 to 2, and p is an integer of 1 to 6)

  Specifically, β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, β- (meth) acryloyloxyethyldimethylmethoxysilane, β- (meth) acryloyloxyethyl Dimethylethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxysilane, γ- (meth) acryloyloxypropyldimethylethoxy Silane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- Meth) acryloyloxy propyl triethoxysilane, and the like.

The silane compound having an allyl group is represented, for example, by the following structural formula (5).
CH ₂ = CHCH ₂ R ² SiR ³ _n (OR ¹ ) _3-n (5)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and R ² and R ³ each have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. Represents an optionally substituted hydrocarbon residue having 1 to 10 carbon atoms, and n is an integer of 0 to 2).

  Specific examples include allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, γ-allylaminopropyltrimethoxysilane, γ-allylaminopropyltriethoxysilane, and the like.

The silane compound having a vinyl group is represented, for example, by the following structural formula (6).
CH ₂ = CHSiR ² _n (OR ¹ ) _3-n (6)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and R ² has 1 carbon atom which may have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. Represents a hydrocarbon residue of -10, n is an integer of 0-2)

  Specific examples include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  The silane compound having a styryl group is represented by the following structural formula (7), for example.

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, R ² represents a hydrogen atom or a methyl group, R ³ represents an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino group. Represents a hydrocarbon residue having 1 to 10 carbon atoms which may have a bond, and n is an integer of 0 to 2).

  Specifically, for example, p-vinylphenylmethyldimethoxysilane, p-vinylphenylmethyldiethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, o-vinylphenyltrimethoxysilane, m- Examples thereof include vinylphenyltrimethoxysilane.

  In addition to the above silane compounds, epoxysilane was allowed to act on the reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and an acid anhydride as described in JP-A-5-247373. ) Acrylic group-containing silane compound, (meth) acrylic group-containing silane in which polyfunctional (meth) acrylate is Michael-added to aminosilane as described in JP-A-3-93372, JP-A-3-207765, etc. Compounds, (meth) acrylic group-containing silane compounds obtained by reacting a hydroxyl group-containing (meth) acrylate and an isocyanate silane as described in JP-A-5-287215 and JP-A-6-10000799 Mercaptosilane, diisocyanate compound, hydroxyl group-containing compounds as described in JP-A-287308 A (meth) acrylic group-containing silane compound reacted with a (meth) acrylate, a mercaptosilane and a polyfunctional (meth) acrylate compound as described in JP-A No. 11-157014 and the like are added by Michael (meta) ) Acrylic group-containing silane compounds and the like can also be used as the radical polymerizable silane compound (s-1) in the present invention.

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

  The non-radically polymerizable silane compound (s-2) used in the present invention is a silane compound that does not have the above-mentioned radical polymerizable group in the molecule, and is involved in the surface modification of the inorganic fine particles (a-3). However, in order not to cause a bond between the thermoplastic resin (a-1) and the inorganic fine particles (a-3), the cured photocurable resin composition (A) is given flexibility and is extremely excellent. It contributes to the provision of high weather resistance and the expression of adhesion to the base sheet (B). Moreover, since it does not accompany a binding reaction, it contributes to the expression of long-term storage stability of the photocurable resin composition and the photocurable sheet.

The non-radically polymerizable silane compound (s-2) is represented by the following structural formula (8), for example.
SiR ² _a R ³ _b (OR ¹ ) _c (8)
(In the above formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and R ² and R ³ each have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. And represents an optionally substituted hydrocarbon residue having 1 to 10 carbon atoms, a and b are each an integer of 0 to 3, and c is an integer of 1 to 4 that satisfies 4-ab.

  Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, Ethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, isobutyltrimethoxysilane, n-octyltrimethoxysilane, n-nonyltrimethoxysilane N-decyltrimethoxysilane, n-undecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, Tadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, eicodecyltrimethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyldimethoxysilane, tetraacetoxysilane , Methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , Γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrime Toxisilane, γ-isocyanatopropyltrimethoxysilane and the like can be mentioned.

  Among them, from the viewpoint of the compatibility with various components such as the thermoplastic resin (a-1) and the solvent in the obtained photocurable resin composition (A) and the dispersion stability of the inorganic fine particles (a-3), The non-radically polymerizable silane compound (s-2) preferably has only a hydrocarbon group.

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

The radically polymerizable silane compound (s-1) and the non-radically polymerizable silane compound (s-2) are 1 mol part of solid content of the inorganic fine particles (a-3) (inorganic fine particles having the number of grams equal to the formula amount of the inorganic fine particles). Therefore, the total amount of the colloidal silica (SiO ₂ = 28 + 16 × 2 = 60) corresponds to 0.001 to 3 mole parts with respect to the solid content of 60 g. It is preferable to do. When the total amount of the silane compound used exceeds 3 mol parts, the abrasion resistance of the resulting photocurable sheet may be lowered. Moreover, when the total amount of silane compounds used is less than 0.0001 mol part, the effect of silane treatment may not be observed.

  The molar ratio of the radically polymerizable silane compound (s-1) to the non-radically polymerizable silane compound (s-2) is preferably in the range of 3:97 to 97: 3, and 5:95 to 95: The range of 5 is more preferable, the range of 10:90 to 90:10 is more preferable, and the range of 10:90 to 80:20 is most preferable. When the use ratio of the radical polymerizable silane compound (s-1) is too large, the adhesion between the layer of the photocurable resin composition (A) and the base sheet (B) is lowered, and further, weather resistance and impact resistance are reduced. Characteristics such as resistance, chipping resistance and long-term storage stability may be deteriorated. Moreover, when there are too many use ratios of a non-radically polymerizable silane compound (s-2), characteristics, such as abrasion resistance, chemical resistance, and transparency, of the photocurable resin composition (A) layer after hardening will fall. There are things to do.

  In the present invention, the inorganic fine particles (a-3) are previously present in the presence of the monomer or hydrolyzate of the radical polymerizable silane compound (s-1) and the non-radical polymerizable silane compound (s-2). It is obtained by subjecting the monomer or hydrolyzate to a hydrolytic condensation reaction.

  Below, an example is demonstrated about the hydrolysis-condensation reaction in presence of an inorganic fine particle (a-3). First, a dispersion solution in which inorganic fine particles (a-3) are dispersed in an appropriate dispersion medium such as alcohol and silane compounds (s-1) and (s-2) are mixed. Subsequently, with respect to 1 mol of the mixture of the silane compounds (s-1) and (s-2), a hydrolysis catalyst such as 0.5 to 6 mol of water or a 0.00001 to 0.1 N hydrochloric acid aqueous solution is used. In addition, alcohol produced by hydrolysis is removed from the system while stirring under heating. Further, the water generated in the condensation reaction following the hydrolysis reaction is similarly removed outside the system under heating, and the condensation reaction is completed.

  The inorganic fine particles (a-3) may be added not only before the hydrolysis / condensation reaction of the silane compound but also during or after the hydrolysis / condensation reaction. This reaction can be carried out under normal pressure or under reduced pressure / pressure. Furthermore, when stirring under heating during the hydrolysis / condensation reaction, the dispersion medium of the inorganic fine particles (a-3) can be substituted with another dispersion medium by azeotropic distillation.

  In the above reaction, an aqueous solution of an inorganic acid or an organic acid can be used as a hydrolysis catalyst. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like are used. Examples of the organic acid include formic acid, acetic acid, oxalic acid, (meth) acrylic acid, and the like.

  Further, it is preferable to use a solvent in order to perform the hydrolysis / condensation reaction gently and uniformly. As this solvent, the dispersion medium of inorganic fine particles (a-3) may be used as it is, or a new solvent may be added in a necessary amount. Examples of the solvent to be newly added include water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone, MEK and MIBK; and ethers such as dioxane and THF.

  Furthermore, the hydrolysis condensation reaction of the inorganic fine particles (a-3) will be specifically described. First, a mixed solution of γ-methacryloyloxypropyltrimethoxysilane and dimethyldimethoxysilane is added to colloidal silica using isopropanol as a dispersion medium, and 0.1N hydrochloric acid aqueous solution is added as a hydrolysis catalyst, followed by stirring under heating. The hydrolysis reaction proceeds. Next, the dispersion medium of colloidal silica is azeotropically distilled together with the nonpolar solvent toluene under reduced pressure, and after the dispersion medium is replaced with toluene, the solid content is within a temperature range of 60 to 150 ° C., preferably 80 to 130 ° C. The mixture is stirred for 0.5 to 10 hours while maintaining the concentration in the range of 30 to 90% by mass, preferably in the range of 40 to 80% by mass.

  The inorganic fine particles (a-3) obtained in this manner are hydrophobized by coating the surface of the fine particles, which were originally hydrophilic, with a silane compound, so that they are in phase with the thermoplastic resin (a-1). Solubility improves, contributes to the improvement of the transparency of a photocurable resin composition, and also contributes to expression of adhesiveness with a base material sheet (B), and expression of long-term storage stability.

  Surface treatment by subjecting the monomer or hydrolyzate of the radical polymerizable silane compound (s-1) and the monomer or hydrolyzate of the non-radically polymerizable silane compound (s-2) to a hydrolysis / condensation reaction The method of adding the inorganic fine particles (a-3) to the thermoplastic resin (a-1) may be a method in which the thermoplastic resin (a-1) is previously synthesized and then dissolved in a solvent, and the inorganic fine particles are mixed. And selecting an arbitrary method such as a method of polymerizing the thermoplastic resin (a-1) under a condition in which the vinyl polymerizable monomer constituting the thermoplastic resin (a-1) and inorganic fine particles are mixed. Can do.

  In the present invention, when the photopolymerizable functional group in the thermoplastic resin (a-1) having a photopolymerizable functional group is an alicyclic epoxy group, the alicyclic epoxy group and the functional group on the surface of the inorganic fine particles ( Hydroxyl groups, carboxyl groups, silanol groups, etc.) may crosslink during mixing and cause gelation. In order to prevent such a gelation phenomenon, it is preferable to include at least one selected from ammonia and an amine compound having a boiling point of 100 ° C. or lower. When forming a photocurable sheet using the photocurable resin composition (A), the boiling point of the amine compound needs to be 100 ° C. or lower so that it does not remain excessively in the sheet.

  Examples of such amine compounds include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and the like.

  Moreover, it is preferable that the addition amount of the said amine compound is the range of 0.01-0.5 mass part with respect to 100 mass parts of solid content of a thermoplastic resin (a-1). From the viewpoint of maintaining the stability of the photocurable resin composition (A), the addition amount is preferably 0.01 parts by mass or more, but if the addition amount exceeds 0.5 parts by mass, the photocurable sheet is insert molded. Even if a molded product obtained by in-mold molding is photocured, photocationic polymerization does not proceed, and scratch resistance and chemical resistance may be inferior.

  In addition to the thermoplastic resin (a-1), the photopolymerization initiator (a-2), and the inorganic fine particles (a-3), the photocurable resin composition (A) includes a sensitizer, as necessary. Additives such as modifying resins, dyes, pigments, leveling agents, anti-repelling agents, ultraviolet absorbers, light stabilizers, and oxidation stabilizers can be blended.

  The above sensitizer accelerates the photocuring reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone.

  Further, when the photopolymerizable functional group in the thermoplastic resin (a-1) is an alicyclic epoxy group, the modifying resin preferably has photocationic polymerizability, a glycidyl ether type epoxy resin, Examples thereof include a glycidyl ester type epoxy resin and a thermoplastic resin having a glycidyl group as an epoxy group.

  However, it is preferable that the photocurable resin composition (A) contains substantially no crosslinkable compound other than the thermoplastic resin (a-1). In particular, a liquid crosslinkable monomer / oligomer which is liquid at 40 ° C. or a low molecular weight crosslinkable monomer / oligomer having a number average molecular weight of 2,000 or less is substantially not contained. If such a liquid or a crosslinkable monomer or oligomer having a number average molecular weight of 2,000 or less is contained, it will have surface tackiness during long-term storage or thermoforming, causing problems in the printing process, Problems such as contamination of the mold during molding or in-mold molding may occur. More preferred are those that substantially contain no liquid crosslinkable monomer or oligomer at 50 ° C, and more preferably those that do not substantially contain a liquid crosslinkable monomer or oligomer at 60 ° C. Here, “substantially does not contain” means that it is not included to the extent that the wear resistance, moldability or storage stability of the resulting photocurable sheet is impaired.

  In the present invention, since the photocurable resin composition (A) as described above is used, the photocurable sheet is formed by laminating the layer of the photocurable resin composition on the base sheet (B). Even in this case, the surface of the photocurable sheet is not sticky, and the phenomenon that the stickiness of the surface changes with time does not occur, and the storage stability in the roll state is improved.

  The thickness of the layer of the photocurable resin composition (A) is preferably in the range of 1 to 50 μm, and more preferably in the range of 2 to 30 μm. When the thickness of the layer of the photocurable resin composition (A) is less than 1 μm, even if the photocurable resin composition (A) is cured, characteristics such as scratch resistance, abrasion resistance, chemical resistance, etc. May decrease. Moreover, when the thickness of a photocurable resin composition (A) layer exceeds 50 micrometers, since a curing defect occurs, warm water resistance and a weather resistance may fall.

  As a method for producing a photocurable sheet of the present invention, for example, a photocurable cast liquid composition obtained by sufficiently stirring and dissolving a photocurable resin composition (A) in a solvent (S) such as an organic solvent is used as a gravure. Known printing methods such as printing method, screen printing method, offset printing method, blade coating method, rod coating method, roll doctor coating method, knife coating method, comma coating method, reverse roll coating method, transfer roll coating method, kissing After coating on the base sheet (B) by a known coating method such as a roll coating method, a curtain coating method, a dip coating method, etc., followed by heat drying for removing the solvent (S), if necessary There is a method of temporarily attaching the cover film onto the photocurable resin composition (A).

  As said solvent (S), each component of a photocurable resin composition (A) is melt | dissolved or disperse | distributed uniformly, and the physical properties (mechanical strength, transparency, etc.) of a base material sheet (B) are practically used. Volatile solvent having no significant adverse effect and having a boiling point of + 80 ° C. or lower, preferably + 30 ° C. or lower, from the glass transition temperature of the resin component (b), which is the main component of the base sheet (B). If it is, it will not be restrict | limited in particular. Examples of such solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol, aromatic solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as hexane and pentane, Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride, phenol solvents such as phenol and cresol, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone, diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 , 2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, ether solvents such as THF, fatty acid solvents such as formic acid, acetic acid, propionic acid, acetic anhydride, etc. Acid anhydride solvent, ethyl acetate, butyl acetate, Ester solvents such as butyl acid, nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide, sulfur-containing solvents such as thiophene and dimethyl sulfoxide, diacetone alcohol, 2-methoxyethanol (methylcellosolve), 2-ethoxy Use a solvent having two or more functional groups such as ethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, or various known solvents such as water. be able to.

  As the base sheet (B) used in the present invention, a suitable one is selected depending on the method of use. For example, ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) is used. Resin, vinyl chloride resin, polystyrene resin, polyolefin resin such as polypropylene, fluorine resin, cellophane resin, cellulose resin, polyurethane resin, polyamide resin such as nylon, polyester resin, polycarbonate resin, Examples thereof include a sheet made of a material such as polyvinyl alcohol resin, ethylene vinyl alcohol resin, or soft acrylic resin. Moreover, the composite of these each sheet | seat, a laminated body, etc. can also be used. Moreover, well-known surface treatments such as corona discharge treatment, plasma discharge treatment, and glow discharge treatment can be applied to the surface of each sheet. Among them, a thermoplastic resin sheet having an elongation of 100% or more when heated at 100 ° C. is preferable because the followability to the mold shape becomes good during insert molding or in-mold molding. In view of adhesion to the photocurable resin composition (A), weather resistance, transparency, and the like, a thermoplastic acrylic resin sheet is further preferable, and a thermoplastic acrylic resin sheet having a crosslinked rubber component is more preferable. Transparent thermoplastic acrylic resin sheets having a crosslinked rubber component are disclosed in JP-A-8-323934, JP-A-9-263614, JP-A-11-147237, JP-A-2001-10474, and the like. There is a transparent thermoplastic acrylic sheet. Commercially available transparent thermoplastic acrylic sheets include Acryprene HBX-N47, HBS-006, HBD-013 (manufactured by Mitsubishi Rayon Co., Ltd.), Technoloy S001, S003, SN101 (summer, Sumitomo Chemical Co., Ltd.) Product), Sanduren SD007, SD009 (manufactured by Kaneka Chemical Co., Ltd.).

  The thickness of the base sheet (B) is preferably 500 μm or less, and more preferably 25 to 500 μm. When the thickness is 100 μm or more, a sufficient depth can be obtained as the appearance of the molded product. In particular, when molding into a complicated shape, a sufficient thickness can be maintained even if the film is stretched. In addition, the upper limit of these ranges is that the rigidity is moderately suppressed to maintain good laminating properties and secondary processability, the mass per unit area is suppressed to maintain economy, and the base material is more stable. This is significant in terms of manufacturing a sheet.

  Moreover, in order to form a coating film having a sufficient thickness on a molded product by coating, it is necessary to perform overcoating a dozen times, which is costly and extremely deteriorated in productivity. If it is a laminated molded product having a photocurable sheet using a base sheet with such a thickness as the outermost layer, the base sheet itself becomes a coating film, so a very thick coating film can be easily formed. Industrially advantageous.

  Further, in the base sheet (B), lubricants such as polyethylene wax and paraffin wax, lubricants such as silica, spherical alumina, and flaky alumina, benzotriazole, benzophenone, and triazine, as appropriate, are included in the base sheet (B). Various additives such as a UV stabilizer such as a cyanoacrylate, a cyanoacrylate, and a fine particle cerium oxide, a light stabilizer such as a hindered amine radical scavenger, a plasticizer, a stabilizer, and a colorant may be added.

  The photocurable sheet of the present invention has a structure in which a layer of the photocurable resin composition (A) is laminated on the base sheet (B), and is not only excellent in workability during insert molding or in-mold molding. It is a photocurable sheet capable of giving a molded article having excellent physical properties (particularly weather resistance-surface hardness (abrasion resistance, pencil hardness) -adhesion balance). As long as the excellent properties of the photocurable sheet of the present invention are not impaired between the photocurable resin composition (A) layer and the base sheet (B), one or more layers of the photocurable resin composition are further provided. It is also possible to stack physical layers. In this case, when a composition equivalent to or similar to the photocurable resin composition (A) is used as the one or more layers of the photocurable resin composition to be newly introduced, the surface properties of the photocurable sheet after photocuring ( In particular, the adhesiveness, weather resistance, appearance, and design properties tend to be favorable, which is preferable.

  The photocurable sheet of the present invention can be a photocurable decorative sheet by providing a printing layer on the base sheet side.

  The printed layer is for decorating the surface of the molded product with patterns, characters, and the like. The decoration is arbitrary, but for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, full-color solid, and the like can be mentioned. Materials for the printing layer include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose A colored ink containing a resin such as an ester resin, an alkyd resin, or a chlorinated polyolefin resin as a binder and a pigment or dye of an appropriate color as a colorant may be used.

  As the ink pigments used in the printing layer, for example, the following can be used. Usually, as pigments, azo pigments such as polyazo as yellow pigments, organic pigments such as isoindolinone, inorganic pigments such as yellow lead, azo pigments such as polyazo as red pigments, organic pigments such as quinacridone, and petals Inorganic pigments such as phthalocyanine blue, cobalt blue and other inorganic pigments, black pigments such as aniline black, and white pigments such as titanium dioxide can be used.

  Various known dyes can be used as the dye of the ink used in the printing layer as long as the effects of the present invention are not impaired.

  As the ink printing method, a known printing method such as an offset printing method, a gravure rotary printing method or a screen printing method, or a known coating method such as a roll coating method or a spray coating method may be used. At this time, as in the present invention, instead of using a low molecular weight crosslinkable compound, when a photocurable resin composition having a structure in which polymers are crosslinked with each other, the surface is not sticky and printing is performed. There are few troubles, and the yield is good.

  Moreover, as a layer for decorating the surface of the molded product, a vapor deposition layer may be provided instead of the print layer, or both the print layer and the vapor deposition layer may be provided.

  The deposited layer uses at least one metal selected from the group of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, or an alloy or compound of these metals. And it can form by methods, such as a vacuum evaporation method, sputtering method, an ion plating method, and a plating method.

  The thickness of the printing layer and the vapor deposition layer for decorating may be appropriately selected according to the degree of expansion at the time of molding so that the desired surface appearance of the molded product can be obtained.

  Moreover, the photocurable sheet | seat of this invention can be used as the photocurable decoration sheet by which the printing layer and / or the vapor deposition layer, the contact bonding layer, and the primer sheet as needed were formed in the base material sheet side. In that case, the preferable thickness range of a photocurable decorating sheet is 25-750 micrometers. When the sheet thickness is less than 25 μm, the sheet thickness on the curved surface is remarkably lowered when deep drawing is performed, and as a result, the sheet physical properties such as scratch resistance and chemical resistance may be lowered. In addition, when the sheet thickness exceeds 750 μm, the shape followability to the mold may be deteriorated.

  As the adhesive layer, any synthetic resinous material can be selected and used as long as it has the property of improving the adhesion between the printed layer or vapor-deposited layer and the molding resin, or the printed layer or vapor-deposited layer and the primer sheet. . For example, when the molding resin is a polyacrylic resin, a polyacrylic resin may be used. If the molding resin is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide resin that has an affinity for these resins A resin or the like may be used. Furthermore, when the molding resin is a polyolefin resin such as a polypropylene resin, heat using chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, or blocked isocyanate A curable urethane resin or the like can be used. In addition, hydrophobic silica, an epoxy resin, a petroleum resin, or the like can be further included for the purpose of reducing the tackiness of the adhesive layer or improving the heat resistance.

  The primer sheet is formed as necessary, and a known resin such as a urethane resin can be used as the material thereof. In addition, it is good to consist of a material compatible with molding resin for the purpose of improving adhesiveness with molding resin. Actually, the primer sheet is preferably made of the same polymer material as the molding resin. The presence of the primer sheet provides the advantage that the surface defects of the injection-molded product are minimized on the photocurable resin composition. In this case, the primer sheet should have a thickness that can absorb the surface defects of the molding resin while exhibiting a completely smooth upper surface of the photocurable resin composition.

  Moreover, a cover film can also be provided in the photocurable sheet of this invention on the photocurable resin composition (A) layer on a base material sheet (B). This cover film is effective for preventing dust on the surface of the photocurable sheet and also effective for preventing scratches on the surface of the photocurable resin composition (A) layer before light irradiation. Furthermore, the temporary attachment of the cover film is also preferable from another viewpoint, that is, the suppression of the decrease in yield and the decrease in handleability due to the decrease in the mechanical strength of the photocurable sheet. Specifically, the mechanical strength of the photocurable sheet may be reduced by the various solvents used in producing the photocurable sheet swelling and dissolving a part of the base sheet (B). . This decrease in mechanical strength often induces an industrial problem by inducing sheet breakage in the subsequent process, leading to a decrease in manufacturing yield, and sheet handling properties. Therefore, by temporarily attaching the cover film, the mechanical strength of the photocurable sheet can be reinforced and the handleability of the sheet can be improved.

  As will be described later, the cover film adheres to the photocurable resin composition (A) layer until insert molding or in-mold molding, and immediately peels off when insert molding or in-mold molding. It is necessary to have appropriate adhesion and good releasability to the conductive resin composition (A) layer. Any film can be selected and used as long as it satisfies such conditions. Examples of such a film include a polyethylene film, a polypropylene film, and a polyester film.

  When the photocurable sheet and the photocurable decorative sheet of the present invention are laminated on a two-dimensional shape, 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. When laminating on a three-dimensional object, a known method such as an insert molding method or an in-mold molding method can be used, and the in-mold molding method is preferred from the viewpoint of productivity. In addition, when the photocurable sheet has a sufficient thickness, the photocurable sheet alone can be formed into a three-dimensional shaped product by a method such as vacuum forming.

  Next, an example of the manufacturing method of the molded article which laminated | stacked said photocurable sheet and photocurable decorating sheet is demonstrated.

  First, when a cover film is provided on a photocurable sheet or a photocurable decorative sheet, the cover film is peeled off from the sheet. The cover film may be peeled off immediately before the sheet is inserted and arranged in the injection mold, or may be peeled off long before the sheet is inserted and arranged in the injection mold. However, the former is preferable in consideration of dust prevention and damage prevention of the photocurable resin composition (A) layer before light irradiation.

  In addition, when the shape of the molded product is not complicated, a resin in which a photocurable sheet or a photocurable decorative sheet on which a cover film is temporarily attached is disposed on the surface by performing injection molding described later without peeling the cover film It is also possible to peel the cover film after obtaining a molded body and then irradiating with light. It is also possible to peel the cover film before light irradiation after injection molding.

  Next, the photocurable sheet or the photocurable decorative sheet is placed so that the photocurable resin composition (A) side faces the inner wall surface of the mold (that is, opposite to the photocurable resin composition (A) layer) Inserted and placed with the side in contact with the molding resin. At this time, a necessary part may be intermittently sent as it is (e.g., unwinding from a roll) as a long sheet, or the sheets may be separated into sheets and fed one by one. In particular, when using a long sheet with a printing layer or vapor deposition layer for decoration, use a feeding device that has a positioning mechanism so that the registration of the layer for decoration matches the mold. Good. In addition, when the sheet is intermittently fed, if the sheet is fixed after the position of the sheet is detected by a sensor, the sheet can always be fixed at the same position, and the position of the layer for decoration is shifted. This is convenient because it does not occur.

  Next, if necessary, a photocurable sheet or a photocurable decorative sheet is preformed.

  For example, the sheet is preliminarily formed by softening the sheet to the softening point or higher by a heating means such as a hot pack and following the sheet to the mold shape by vacuum suction through a suction hole provided in the injection mold. Can do. In addition, by using a three-dimensional processing mold different from the injection mold, in advance, by a known molding method such as a vacuum molding method, a pressure molding method, a pressure molding method for pressing heated rubber, or a press molding method. The sheet may be preformed in a desired shape in advance, and unnecessary portions may be removed and then loaded into an injection mold. If the sheet is preheated to a temperature lower than the thermal deformation temperature of the sheet before the sheet is inserted into the mold, the heating time to be performed after the sheet is inserted into the mold can be shortened. It becomes possible to improve productivity.

  Of course, it is also possible to simultaneously perform the molding of the sheet and the integration with the molding resin by the injection pressure of the molding resin described later without preforming the sheet. At this time, the sheet can be preheated and softened in advance.

  Thereafter, the mold is closed, a molten molded resin is injected into the cavity, and the resin is solidified to form a resin molded body in which the photocurable sheet or the photocurable decorative sheet is disposed on the surface. .

  Thus, when giving a three-dimensional shape to a photocurable sheet | seat by vacuum forming, the photocurable sheet | seat of this invention is rich in the elongation at the time of high temperature, and is very advantageous.

  As the molding resin used in the present invention, any resin that can be injection molded can be used regardless of the type. Examples of such molding resins include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymer resins, and olefin thermoplastics. Olefin resins such as elastomers, polystyrene resins, ABS (acrylonitrile / butadiene / styrene copolymers) resins, AS (acrylonitrile / styrene copolymers) resins, acrylic resins, urethane resins, unsaturated polyesters And general-purpose thermoplastic or thermosetting resins such as epoxy resins and epoxy resins. Also, general-purpose engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, polycarbonate modified polyphenylene ether resins, polyethylene terephthalate resins, polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyethers Super engineering resins such as imide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat resistant resins can also be used. Further, reinforcing materials such as glass fibers and inorganic fillers (talc, calcium carbonate, silica, mica, etc.), composite resins added with modifiers such as rubber components, and various modified resins can be used. It is preferable that the shrinkage rate after molding of the molding resin is approximated to the shrinkage rate of the sheet because problems such as warpage of the molded product and peeling of the sheet can be eliminated.

  Finally, after taking out the molded product from the mold, the photocurable resin composition on the surface of the molded product is photocured by light irradiation.

Examples of light to be irradiated include electron beams, ultraviolet rays, and γ rays. Although irradiation conditions are determined according to the photocuring property of a photocurable resin composition (A) layer, irradiation amount is about 500-10,000mJ / cm < ² > normally. As a result, a molded product in which the photocurable resin composition is cured and a hard film is formed on the surface can be obtained.

  Of the photocurable sheet or photocurable decoration adhered to the molded product, unnecessary portions are appropriately trimmed and removed as necessary. This trimming can be performed after the sheet is inserted and placed in the mold, before the molded product is irradiated with light, or after irradiated with light. As a trimming method, a known method, such as a method of burning a sheet by irradiating a laser beam or the like, a method of producing a punching die for trimming, punching a sheet by press working, a method of removing the sheet by tearing manually, etc. Can be performed.

  Molded articles of the present invention include weather strips, bumpers, bumper guards, side mud guards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, etc. , Automotive exterior applications such as headlamp covers, taillight covers, windshield parts, instrument panels, console boxes, meter covers, door lock bezels, steering wheels, power window switch bases, center clusters, dashboards, automotive interior applications, AV Applications such as front panels of equipment and furniture products, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as walls, ceilings, and floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreaks, furniture such as window frames, doors, railings, sills, and duck Use for surface cosmetic materials such as interior materials for automobiles, use for various displays, lenses, mirrors, goggles, window glass and other optical components, or interior and exterior use for various vehicles other than automobiles such as trains, aircraft, ships, bottles, cosmetic containers, It can be suitably used for various packaging containers and materials such as small items, and various other uses such as miscellaneous goods such as prizes and small items. In addition, on transparent resin, a surface with good wear resistance, weather resistance, and chemical resistance can be formed while taking advantage of its transparency, and windows, headlamp covers, windshields of automobiles, railway vehicles, airplanes, etc. It can be suitably used for parts and the like. In addition, the number of steps can be omitted compared to the case where the surface of the molded product is painted, the productivity is good, and the influence on the environment is small.

  In the above description, a manufacturing method using injection molding has been described as a manufacturing method of a molded product, but blow molding may be used instead of injection molding.

  The molded product thus obtained is given a color or design at the same time as molding, and is further improved in wear resistance, chemical resistance, weather resistance, etc. by light irradiation for a short time. Furthermore, the process can be shortened, the yield can be improved, and the impact on the environment can be reduced as compared with conventional spray coating after molding. In particular, the photocurable sheet of the present invention is excellent in processability and storage stability, has no surface tackiness, and has good adhesion between the layer of the photocurable resin composition and the base sheet, industrial The practical use value is extremely high.

The present invention will be specifically described below based on examples. In the examples, “parts” means “parts by mass”. Abbreviations in the examples are as follows.
Methyl methacrylate MMA
n-octyl mercaptan nOM
Methyl ethyl ketone MEK
Glycidyl methacrylate GMA
Azobisisobutyronitrile AIBN
Hydroquinone monomethyl ether MEHQ
Triphenylphosphine TPP
Acrylic acid AA

Synthesis Example 1 (Synthesis of acrylic resin A having a photopolymerizable functional group in the side chain as component (a-1))
50 parts of MEK was put into a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 100 parts GMA, 0.5 parts AIBN and 1 part nOM was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of MEK and 0.2 part of AIBN was added and polymerized. After 4 hours, 50 parts of MEK, 0.5 part of MEHQ, 2.5 parts of TPP, and 50.1 parts of AA were added and stirred at 80 ° C. for 30 hours while blowing air. Then, after cooling, the reaction product was taken out from the flask to obtain a solution of acrylic resin A having a photopolymerizable functional group in the side chain.

  The polymerization rate of the monomer in the acrylic resin A having a photopolymerizable functional group in the side chain is 99.5% or more, the polymer solid content is about 46% by weight, the number average molecular weight is about 25,000, and the glass transition temperature. Was about 32 ° C., and the average double bond equivalent was 216 g / mol.

Synthesis Example 2 (Synthesis of acrylic resin B having a photopolymerizable functional group on the side chain as component (a-1))
In a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 100 parts of 3,4-epoxycyclohexylmethyl methacrylate, 60 parts of MEK and 0.3 part of AIBN are placed in a nitrogen atmosphere and stirred. While raising the temperature of the hot water bath to 75 ° C., polymerization was carried out at that temperature for 2 hours. Then, 0.7 parts of AIBN was added in 5 portions every 1 hour, and then the temperature in the flask was raised to the boiling point of the solvent and polymerization was conducted at that temperature for another 2 hours. Thereafter, after the temperature in the flask became 50 ° C. or less, 90 parts of MEK was added and the polymerization reaction product was taken out of the flask to obtain a solution of acrylic resin B having a photopolymerizable functional group in the side chain.

  The polymerization rate of the monomer in the acrylic resin B having a photopolymerizable functional group in the side chain is 99.5% or more, the polymer solid content is about 40% by weight, the number average molecular weight is about 12,000, the glass transition temperature. Was about 73 ° C., and the alicyclic epoxy equivalent (average molecular weight per side chain alicyclic epoxy group) was 196 g / mol on average.

Synthesis Example 3 (Synthesis of acrylic resin C having a photopolymerizable functional group in the side chain as component (a-1))
50 parts of MEK was put into a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 79.9 parts of MMA, 20.1 parts of GMA and 0.5 part of AIBN was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of MEK and 0.2 part of AIBN was added and polymerized. After 4 hours, MEK 74.4 parts, MEHQ 0.5 parts, TPP 2.5 parts and AA 10.1 parts were added and stirred at 80 ° C. for 30 hours while blowing air. Then, after cooling, the reaction product was taken out from the flask to obtain a solution of a thermoplastic resin C having a photopolymerizable functional group in the side chain.

  The polymerization rate of the monomer in the thermoplastic resin C having a photopolymerizable functional group in the side chain is 99.5% or more, the polymer solid content is about 35% by mass, the number average molecular weight is about 30,000, glass transition The temperature was about 105 ° C., and the average double bond equivalent was 788 g / mol.

Surface treatment example 1 of colloidal silica (Preparation of surface-treated colloidal silica CS1)
In a flask equipped with a stirrer, a condenser and a thermometer, 630 parts of IPA-ST (isopropanol-dispersed colloidal silica sol, manufactured by Nissan Chemical Industries, silica particle diameter 15 nm, silica solid content 30% by mass) and MEHQ0. 012 parts, 50 parts of a 0.0001N aqueous hydrochloric acid solution as a hydrolysis catalyst was added, and the temperature of the hot water bath was raised to 80 ° C. while stirring. At the same time as refluxing, 117.2 parts of γ-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM503, molecular weight 248), trimethylmethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name LS) -510, molecular weight 104) 16.4 parts of a mixed solution was added dropwise over about 30 minutes. After the addition was completed, the mixture was dispersed in isopropanol by heating and stirring for about 2 hours, and the surface was treated with a silane compound. Colloidal silica was obtained.

  Subsequently, while the temperature of the hot water bath was raised to 110 ° C., isopropanol was distilled off and toluene was repeatedly added. Over about 4 hours, isopropanol was completely replaced with toluene, and the solid content concentration was 40% by mass. By concentrating until obtained, colloidal silica CS1 dispersed in toluene and treated with a silane compound was obtained.

Surface treatment examples 2 to 14 of colloidal silica (Preparation of surface treatment colloidal silica CS2 to CS13 and preparation of CS14)
Colloidal silica CS2 dispersed in toluene and treated with a silane compound in the same manner as in the case of colloidal silica CS1, except that the combination of each component was changed as shown in Table 2 below. ~ CS13 was obtained.

  Further, as CS14, a commercially available MEK-dispersed colloidal silica was used as it was without performing the same operation as CS1.

  Note) The numerical value is the mole part in terms of solid content.

1) IPA-ST: Isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle size = 15 nm, silica solid content = 30% by mass
2) 3MPTMS: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-503, molecular weight = 248
3) TMMS: Trimethylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name LS-510, molecular weight = 104
4) PTMS: Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-103, molecular weight = 198
5) nDTMS: n-decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-3103C, molecular weight = 263
6) 3GPTMS: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-403, molecular weight = 236
7) 3MRPTMS: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-803, molecular weight = 196
8) VTMS: Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-1003, molecular weight = 148
9) STMS: p-styryltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name KBM-1403, molecular weight = 224
10) MEK-ST: MEK-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle diameter = 15 nm, silica solid content = 30% by mass

Preparation of photocurable casting liquid composition (Preparation of photocurable casting liquid compositions 1 to 16)
A photocurable casting liquid composition 1 having the composition shown in Table 3 below using the synthesized acrylic resins A to C having a photopolymerizable functional group in the side chain, surface-treated colloidal silica CS1 to CS14, and the compounds shown in Table 3 below. ~ 16 were prepared.

  Note) Numerical values are parts by mass in terms of solid content.

1) 1-hydroxycyclohexyl phenyl ketone 2) triphenylsulfonium hexafluoroantimonate

  The prepared photocurable casting liquid composition was sealed in a metal container, and the state after storage for 3 months in an environment of 50 ° C. was visually evaluated. The results are shown in Table 3.

  Photocurable cast liquid compositions 1 to 13 containing colloidal silica treated with two types of silane compounds, a radically polymerizable silane compound and a non-radically polymerizable silane compound, did not change with time such as thickening, and immediately after preparation. The situation was almost the same.

  On the other hand, the photocurable cast liquid compositions 14 and 15 containing colloidal silica treated with a single silane compound and the photocurable cast liquid composition 16 containing untreated colloidal silica have increased casting liquid viscosity. The storage stability was found to be low.

Example 1
The obtained photocurable casting liquid composition 1 was stirred with a propeller-type mixer, and coated on a commercially available acrylic sheet (Mitsubishi Rayon Co., Ltd., Acryprene HBX-N47, thickness 125 μm, width 730 mm) with a comma roll coater. Coating was performed at a work width of 690 mm.

  Subsequently, the tunnel-type drying furnace (width 800 mm, height 100 mm, length 8 m, divided into four drying zones (one zone length 2 m)) set to the temperature conditions shown in Table 4 below is suitable for sheet movement. The solvent was volatilized by passing it through a method in which hot air was fed so as to be a flow, and a sheet support method was a roll support method) to form a photocurable resin layer having a thickness of 8 μm. Table 4 shows the residence time of each drying zone at this time.

  Subsequently, the PET film subjected to the fine adhesion treatment was used as a cover film, and the cover film was bonded in-line so that the fine adhesion layer of the PET film and the photocurable resin layer were in contact with each other and passed through a press roll, and the length was 1000 m. It wound up in roll shape on the core made from ABS.

  In this roll state, it was stored for 3 months in an atmospheric temperature of 50 ° C. under a fluorescent lamp without taking light shielding measures.

  After storage, a part of the photocurable sheet was unwound, the cover film was peeled off by hand, and the state of the photocurable resin layer surface was observed. The surface of the photocurable resin layer was good without any design defects. The results are shown in Table 5.

  Subsequently, the photocurable sheet was made into a single sheet, the cover film was peeled off by hand, and the photocurable resin composition was placed in the mold so as to face the inner wall surface of the mold, and then an infrared heater (temperature The sheet was preheated at 350 ° C. for 10 seconds, and then the sheet was caused to follow the mold shape by vacuum suction while further heating. The shape of this mold is a truncated pyramid, the size of the truncated surface is 100 mm × 100 mm, the size of the bottom surface is 108 mm × 117 mm, the depth is 10 mm, and the radius of curvature of the edge of the truncated surface is Were 3, 5, 7, and 10 mm, respectively. When the mold following property at that time was visually evaluated, each end portion followed well.

  Next, in-mold molding is performed using a polycarbonate resin as a molding resin under conditions of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C., thereby obtaining a molded product in which the photocurable sheet is in close contact with the surface of the molded product. It was. At this time, the stain on the molding die was visually evaluated. The results are shown in Table 5.

Next, using an ultraviolet irradiation device, ultraviolet rays of about 700 mJ / cm ² were irradiated to cure the photocurable resin composition, and the surface physical properties were evaluated. As shown in Table 5, the appearance of the molded product was very good, and other surface properties were also good.

Molded article physical property evaluation method Appearance evaluation: Visually evaluated.

  Pencil hardness test: According to JIS K 5400, evaluation was performed using Uni (Mitsubishi Pencil Co., Ltd .; trade name) as a pencil.

Cross-cut peel test: According to JIS K 5400, 100 square grids having a width of 1 × 1 mm were prepared with a cutter, and Nichiban-made cello tape was pressure-bonded, and the film appearance after peeling at a 90-degree angle was visually evaluated ( Cross peelability 1). Further, the appearance of the film after repeating the pressure-bonding / peeling of the cello tape at the same site for a total of 5 times was visually evaluated (cross-cut peelability 2).
○: No change in appearance △: Peeling around the grid or slight peeling of the grid *: Peeling around the grid and / or peeling of the grid

Acid resistance: The appearance after a spot test of a 47% by weight sulfuric acid aqueous solution at 40 ° C. for 3 hours was visually evaluated.
○: Good △: Thin trace x: Remarkable trace

Alkali resistance: The appearance after a spot test of a 0.1 N aqueous sodium hydroxide solution at 55 ° C. for 4 hours was visually evaluated.
○: Good △: Thin trace x: Remarkable trace

Hot water resistance: The sheet state after immersion in warm water of 40 ° C. for 24 hours was visually evaluated.
○: Good △: Thin whitening ×: Remarkable whitening

  Transparency: The total light transmittance and haze were measured using a haze meter according to ASTM D1003.

  Abrasion resistance: The haze value was measured with a haze meter after the Taber abrasion test (500 g load on one side, CS-10F wear wheel was used, and the test was carried out at a rotational speed of 60 rpm and 100 tests). And the numerical value represented by (the haze value after the test) − (the haze value before the test) was shown as wear resistance (%).

Weather resistance: A sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) was used to visually evaluate the appearance when the exposure test was performed for 4000 hours in a cycle of 48 minutes for drying and 12 minutes for rain.
○: Good △: Slightly whitened and gloss decreased ×: Whitened or cracked

Examples 2-13
A photocurable sheet was produced in the same manner as in Example 1 except that the photocurable casting liquid composition 1 of Example 1 was changed to the combination shown in Table 5, and an in-mold molded product was obtained. In any of the photocurable sheets, the photocurable resin composition layer had no surface tackiness, and no design defects were observed after the cover film was peeled off. Moreover, all in-mold molded products showed good surface properties. The results are shown in Table 5.

Comparative Examples 1-3
A photocurable sheet was produced in the same manner as in Example 1 except that the photocurable cast liquid composition 1 of Example 1 was changed to the combination shown in Table 5, and an in-mold molded product was obtained.
None of the photocurable sheets have the surface tackiness of the photocurable resin composition layer, but the obtained in-mold molded product has microcracks on the curved surface of the molded product, which can be stored during long-term storage. It was observed that the elongation of the photocurable sheet was reduced. Further, the adhesion, weather resistance, and chemical resistance of the flat part of the molded product were also inferior. The results are shown in Table 5.

Examples 14-26
In the same manner as in Examples 1 to 13, a photocurable sheet in which the cover film was temporarily attached to the photocurable resin layer was produced.

  Next, using an ink composed of pigments of black, brown, and yellow, a pattern was printed on the surface of the base sheet by a gravure printing method, and a photocurable decorative sheet was obtained.

  After these photocurable decorative sheets are made into a single sheet and the cover film is peeled off, the photocurable resin composition is placed in the mold so as to face the inner wall surface of the mold, and then an infrared heater (temperature of 300 ° C.) After the sheet was preheated for 15 seconds, the sheet was allowed to follow the mold shape by vacuum suction while further heating.

  Next, under conditions of a molding temperature of 220 to 250 ° C. and a mold temperature of 40 to 60 ° C., in-mold molding is performed using acrylonitrile / butadiene / styrene copolymer resin as a molding resin, and a photocurable decorative sheet is molded. A molded product adhered to the product surface was obtained. The mold following property and mold releasability of the sheet at that time were both good.

Next, by using an ultraviolet irradiation device, the photocurable resin composition is cured by irradiating with an ultraviolet ray of about 700 mJ / cm ² , forming with high surface hardness, excellent gloss, and having a printed pattern and excellent design. I got a product.

Examples 27-39
In the same manner as in Examples 1 to 13, a photocurable sheet in which the cover film was temporarily attached to the photocurable resin layer was produced.

  Subsequently, the ink which consists of a pigment of each color of black, brown, and yellow was used, and the pattern was printed on the base material sheet surface by the gravure printing method.

  Furthermore, after forming the adhesive layer which consists of chlorinated polypropylene resin (chlorination degree 15%) by the gravure printing method on the printing surface, the photocurable decorating sheet was obtained.

  After these photocurable decorative sheets are made into a single sheet and the cover film is peeled off, the photocurable resin composition is placed in the mold so as to face the inner wall surface of the mold, and then an infrared heater (temperature of 300 ° C.) After the sheet was preheated for 15 seconds, the sheet was allowed to follow the mold shape by vacuum suction while further heating.

  Next, under conditions of a molding temperature of 200 to 240 ° C. and a mold temperature of 30 to 60 ° C., a polypropylene resin (containing 20% by weight of talc and 10% by weight of ethylene-propylene rubber) is used as a molding resin. Molding was performed to obtain a molded product in which the photocurable decorative sheet was in close contact with the surface of the molded product. The mold following property and mold releasability of the sheet at that time were both good.

Next, using an ultraviolet irradiation device, the photocurable resin composition is cured by irradiating ultraviolet rays of about 700 mJ / cm ² , has high surface hardness and high wear resistance, excellent gloss, and has a printed pattern. A molded product excellent in design was obtained.

  The present invention can provide a molded article having excellent appearance, design, abrasion resistance, chemical resistance and weather resistance, is excellent in long-term storage stability, and is a photocurable sheet having no surface tackiness, and A molded product using this sheet can be provided, which is industrially useful.

Claims (13)

  A photocurable resin composition comprising a thermoplastic resin (a-1) having a photopolymerizable functional group, a photopolymerization initiator (a-2), and inorganic fine particles (a-3), wherein the inorganic fine particles (a -3) is a monomer or hydrolyzate of a radically polymerizable silane compound (s-1) and a monomer or hydrolyzate of a non-radically polymerizable silane compound (s-2) in the presence thereof. And a photo-curable resin composition obtained by hydrolytic condensation reaction.   The photocurable resin composition of Claim 1 whose thermoplastic resin (a-1) which has a photopolymerizable functional group is an acrylic resin which has a photopolymerizable functional group in a molecule | numerator.   The photocurable resin composition of Claim 1 whose thermoplastic resin (a-1) which has a photopolymerizable functional group is an acrylic resin which has a photopolymerizable functional group in a side chain.   The photocurable resin composition in any one of Claims 1-3 in which a photocurable resin composition does not contain crosslinkable compounds other than the said resin (a-1) substantially.   The photocurable resin composition according to any one of claims 1 to 4, wherein the inorganic fine particles (a-3) are colloidal silica.   The photocurable sheet which has a layer of the photocurable resin composition (A) in any one of Claims 1-5 on a base material sheet (B).   The photocurable sheet according to claim 6, wherein the base sheet (B) is a thermoplastic acrylic resin sheet.   The photocurable sheet according to claim 7, wherein the base sheet (B) is a thermoplastic acrylic resin sheet having a crosslinked rubber component.   A photocurable additive in which at least one layer selected from a printed layer, a vapor deposition layer, an adhesive layer and a primer layer is formed on the base sheet (B) side of the photocurable sheet according to any one of claims 6 to 8. Decorative sheet.   A step of inserting and arranging the photocurable sheet or photocurable decorative sheet according to any one of claims 6 to 9 so that the photocurable resin composition (A) side faces the inner wall surface of the mold, , By injecting molten resin into a mold and solidifying the resin to form a resin molded product having a photocurable sheet or photocurable decorative sheet disposed on the surface, and light irradiation The manufacturing method of a molded article including the process of photocuring the photocurable resin composition of the molded article surface by.   A step of inserting and arranging the photocurable sheet or photocurable decorative sheet according to any one of claims 6 to 9 such that the photocurable resin composition (A) side faces the inner wall surface of the mold, photocuring A step of preforming an adhesive sheet or a photocurable decorative sheet and following the mold shape, closing the mold, injecting molten resin into the mold, and solidifying the resin, the photocurable sheet Or the manufacturing method of the molded article including the process of photocuring the photocurable resin composition of the surface of a molded article by light-irradiating the process of forming the resin molded article in which the photocurable decorating sheet has been arrange | positioned on the surface.   The photocurable sheet or photocurable decorative sheet according to any one of claims 6 to 9 is inserted into a preforming mold so that the photocurable resin composition (A) side faces the inner wall surface of the mold. A step of arranging, a step of preforming a photocurable sheet or a photocurable decorative sheet and causing the sheet to follow the shape of the mold, a preformed photocurable sheet or a photocurable decorative sheet, a photocurable resin A step of inserting and arranging in the molding die so that the composition side faces the inner wall surface of the die, closing the molding die, injecting the molten resin into the die, and solidifying the resin, the photocurable sheet Or the manufacturing method of the molded article including the process of photocuring the photocurable resin composition of the surface of a molded article by light-irradiating the process of forming the resin molded article in which the photocurable decorating sheet has been arrange | positioned on the surface.   The molded product obtained by the manufacturing method in any one of Claims 10-12.