JP2005138584A - Photocurable sheet and molded product using the same - Google Patents

Abstract

[PROBLEMS] To develop a photocurable sheet and a photocurable decorative sheet having excellent appearance, designability, abrasion resistance, chemical resistance, and weather resistance, and having no surface adhesiveness, and a molded product comprising the sheet. To do.
A layer of a photocurable resin composition (A) containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photopolymerization initiator (a-2), and a base sheet (B) A base material sheet (B) is a thermoplastic acrylic resin sheet composed of two or more acrylic resin layers having different thermal deformation temperatures, and is in contact with the photocurable resin composition (A) layer. A photocurable sheet, wherein the heat distortion temperature of the layer is less than 85 ° C. A photocurable decorative sheet in which at least one of a printed layer, a vapor deposition layer, an adhesive layer, and a primer layer is formed on the base sheet side of the photocurable sheet.

Description

  The present invention relates to a photocurable sheet and a method for producing the photocurable sheet. In particular, the present invention has a photocurable sheet having excellent appearance, design, abrasion resistance, chemical resistance and weather resistance, and having no surface tackiness, and a method for producing the same, and molding using the sheet It relates to the manufacturing method of goods.

  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 a very important characteristic.
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 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 base material are laminated is proposed (for example, , See Patent Document 4). However, in this method, since the sheet before photocuring contains a compound having a low molecular weight reactive vinyl group, 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, problems have occurred in the printing process when used as a printing sheet.

  On the other hand, by laminating a composition comprising a photopolymerization initiator and a resin having an alicyclic epoxy group or radical polymerizable unsaturated group in the side chain, it is represented by in-mold molding or insert molding. Excellent wear resistance, weather resistance and chemical resistance that can be advantageously used in the production of molded articles with good design that can be used in the method of (3), and have no tackiness and workability. And the photocurable sheet which has the photocurable resin excellent in storage stability on the surface is disclosed (for example, refer patent document 5, 6). Such a photocurable sheet not only imparts decorativeness to a molded product, but also has a function as an alternative material for coating.

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 2002-79621 A

The photo-curable sheets as described in Patent Documents 5 and 6 are very good for scratching properties such as a wear test when focusing on scratching properties. There is no mention of scratchability assuming a case where a hard object hits locally. In addition, it is generally known that the pencil hardness depends on the hardness of the base sheet itself, but there is no description of the base sheet with respect to the pencil hardness, and in particular, good adhesion (photocurable resin composition). There is no suggestion of a substrate sheet for a photocurable sheet having both a physical layer and a substrate sheet) and a high surface hardness.
Through the process of developing these photocurable sheets, the present inventors have stabilized the photocurable sheet having both good adhesion (between the photocurable resin composition layer and the base sheet) and high surface hardness at the same time. Thus, it has been found that it is necessary to use a specific base material sheet for manufacturing, and thus the present invention has been completed.

That is, the present invention includes a layer of a photocurable resin composition (A) containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photopolymerization initiator (a-2), and a base sheet ( B) a photo-curable sheet, wherein the base sheet (B) is a thermoplastic acrylic resin sheet composed of two or more acrylic resin layers having different thermal deformation temperatures, and the photo-curable resin composition (A) layer. And a photocurable sheet having a heat deformation temperature of less than 85 ° C.
Moreover, this invention provides the photocurable decorating sheet which formed at least 1 layer or more among the printing layer, the vapor deposition layer, the contact bonding layer, and the primer layer in the base material sheet side of the said photocurable sheet.
Furthermore, this invention provides the manufacturing method of the said photocurable sheet and a photocurable decorating sheet, the molded article using the said photocurable sheet or the photocurable decorating sheet, and the manufacturing method of the molded article. It is.

  According to the present invention, a layer of a photocurable resin composition (A) containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photopolymerization initiator (a-2), and a base sheet ( B) a photo-curable sheet, wherein the base sheet (B) is a thermoplastic acrylic resin sheet composed of two or more acrylic resin layers having different thermal deformation temperatures, and the photo-curable resin composition (A) layer. A light curable sheet having a thermal deformation temperature of less than 85 ° C. of the layer in contact with the light, and a light in which at least one of a printed layer, a vapor deposition layer, an adhesive layer, and a primer layer is formed on the substrate sheet side of the photocurable sheet By adopting a curable decorative sheet, it has good adhesion and high surface hardness between the layer of the photocurable resin composition and the base sheet, and has excellent physical properties (abrasion resistance, weather resistance) , Chemical resistance, processability, storage stability, appearance, etc.) Photocuring sheet and excellent molded article design property is provided.

The present invention is described in detail below.
The photocurable sheet of the present invention comprises a layer of a photocurable resin composition (A) containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photopolymerization initiator (a-2), and a group. It is a photocurable sheet composed of a material sheet (B), and the base sheet (B) is a thermoplastic acrylic resin sheet composed of two or more layers of acrylic resin layers having different thermal deformation temperatures, and a photocurable resin composition ( A) It is characterized by comprising a photocurable sheet in which the heat deformation temperature of the layer in contact with the layer is less than 85 ° C.
Thus, the base sheet (B) is a thermoplastic acrylic resin sheet composed of two or more acrylic resin layers having different thermal deformation temperatures, and the thermal deformation temperature of the layer in contact with the photocurable resin composition (A) layer is 85. When the temperature is lower than 0 ° C., it has good adhesion between the layer of the photocurable resin composition and the base sheet and high surface hardness, and has excellent physical properties (abrasion resistance, weather resistance, chemical resistance). A photocurable sheet capable of exhibiting properties, workability, storage stability, appearance, etc.) can be stably produced.

As the thermoplastic resin (a-1) having a photopolymerizable functional group, a compound having two or more photopolymerizable functional groups in one molecule and being cured by a photopolymerization reaction to form a crosslinked body is used. The containing composition 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.
Further, from the viewpoint of weather resistance of the thermoplastic resin (a-1) and expression of adhesion to the base sheet (B) which is a thermoplastic acrylic resin sheet, the thermoplastic resin (a-1) is photopolymerized in the molecule. An acrylic resin having a functional functional group is preferred.
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, a crosslinking reaction proceeds between the side chains, so that good wear resistance is exhibited without containing a low molecular weight crosslinkable compound. In addition, the absence of a low molecular weight crosslinkable compound has the advantage that the sheet surface is not sticky and has excellent storage stability.

The photopolymerizable functional group may be any group that can be polymerized by irradiation with light, but is preferably a radically polymerizable unsaturated group or an alicyclic epoxy group represented by the following structural formula (1). Is 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) Monomers having a sulfone group: 2-acrylamido-2-methylpropanesulfonic acid, etc.

(7) Monomer having an isocyanate group: an adduct of a radically polymerizable monomer having a diisocyanate and an active hydrogen, such as an equimolar adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate, Isocyanate ethyl (meth) acrylate, etc. (8) Furthermore, in order to adjust the glass transition temperature of the above-mentioned copolymer or to harmonize the physical properties of the photo-curable sheet, the above-mentioned compound can be copolymerized with it. It can also be copolymerized with a monomer. 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.

As a thermoplastic resin which has an alicyclic epoxy group in the side chain used for this invention, what has an alicyclic epoxy group in the 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. 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).

（式中、Ｒはメチル基または水素原子を表し、ｎは０〜５の整数である）

(In the 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 an average of 3,000 g / mol or less as calculated from the charged value, from the viewpoint of improving scratch resistance and abrasion resistance. A more preferable range is 1,200 g / mol or less on average, and a most preferable range is 800 g / mol or less on average.
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 number average molecular weight of the thermoplastic resin (a-1) is preferably in the range of 5,000 to 2,500,000. The lower limit is more preferably 10,000 or less. The upper limit is more preferably 1,000,000 or less.
When mold-molding or in-mold molding a photo-curable sheet formed using the photo-curable resin composition (A) containing the thermoplastic resin (a-1), the mold releasability is improved. 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, it is preferable that the number average molecular weight is 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).

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. The upper limit of the glass transition temperature is more preferably 150 ° C. or less. 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 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, heat resistance and the like 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 by light irradiation and a photocationic polymerization initiator that generates an acid. In the case of an unsaturated group, a photo radical polymerization initiator is used, and in the case of an alicyclic epoxy group, a photo cationic 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 An initiator that does not contain an amino group in the molecule is preferable. 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 the temperature may be temporarily higher than the boiling point of the compound depending on the molding method. In order to increase the surface hardness of the molded article, an additive such as n-methyldiethanolamine, which 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 amount of the radical photopolymerization initiator added is 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a-1) having a photopolymerizable functional group in the side chain because the residual amount after curing affects the weather resistance. The following are desirable, and when the radical photopolymerization initiator is an amino radical photopolymerization initiator, the amount is preferably 1 part by mass or less.
As the photocationic polymerization initiator, known compounds can be used, and there are no particular limitations, but specific examples 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.

（式中、Ｒ¹ は炭素−炭素結合もしくは炭素−硫黄結合を介する置換もしくは未置換の芳香族環を表し、Ｒ² 及びＲ³ は、それぞれ、置換あるいは未置換の芳香族環を表す）
光カチオン重合開始剤の添加量は、側鎖に光重合性官能基を有する熱可塑性樹脂（ａ−１）１００質量部に対して０．１〜１０質量部が好ましい。

(Wherein 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)
The addition amount of the cationic photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a-1) having a photopolymerizable functional group in the side chain.

  Inorganic fine particles (a-3) can be 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. Is 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.

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 an organic solvent 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 that can dissolve the thermoplastic resin. However, as will be described later, these organic solvents are used when producing the photocurable sheet of the present invention. Is volatilized by heating and drying, and therefore tends to remain in the photocurable sheet when the boiling point is 80 ° C. or higher than the glass transition temperature of the resin component (b), which is the main component of the base sheet (B). Even at 30 ° C. or higher, a tendency to remain in the photocurable sheet is observed.

  Colloidal silica in a form dispersed in an organic solvent includes commercially available products dispersed in a dispersion medium, such as 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- Commercial products such as ST (trade name, manufactured by Nissan Chemical Co., Ltd.) 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 the inorganic fine particles (a-3) is preferably in the range of 5 to 400 parts by mass in terms of solids of the inorganic fine particles with respect to 100 parts by mass of the 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.

As the inorganic fine particles (a-3), those having a surface treated beforehand with a silane compound represented by the following structural formula (4) may be used. The use of surface-treated inorganic fine particles is preferable because the storage stability of the photocurable resin composition (A) is further improved, and the surface hardness and weather resistance of the resulting photocurable sheet are also improved.
SiR ⁴ _a R ⁵ _B (OR ⁶ ) _c (4)
(In the above formula, R ⁴ and R ⁵ each represent a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond; ⁶ represents a hydrogen atom or an ether bond, an ester bond, an epoxy bond or a carbon-carbon hydrocarbon residue which may have a carbon-carbon double bond, and a and b are 0 to 3 respectively. And c is an integer of 1 to 4 that satisfies 4-ab.

Among the silane compounds represented by the structural formula (4), silane compounds represented by the following structural formulas (5) to (10) can be given as preferable examples.
SiR ⁷ _a R ⁸ _b (OR ⁹ ) _c (5)
SiR ⁷ _n (OCH ₂ CH ₂ OCO (R ¹⁰ ) C═CH ₂ ) _4-n (6)
CH ₂ = C (R ¹⁰ ) COO (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (7)
CH ₂ = CHSiR ¹¹ _n (OR ⁹ ) _3-n (8)
HS (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (9)

（式中、Ｒ⁷ 及びＲ⁸ は、それぞれ、エーテル結合、エステル結合またはエポキシ結合を有していてもよい炭素数１〜１０の炭化水素残基を表し、Ｒ⁹ は水素原子または炭素数１〜１０の炭化水素残基を表し、Ｒ¹⁰は水素原子またはメチル基を表し、Ｒ¹¹は炭素数１〜３のアルキル基またはフェニル基を表し、ａ及びｂは、それぞれ、０〜３の整数であり、ｃは４−ａ−ｂを満足する１〜４の整数であり、ｎは０〜２の整数であり、ｐは１〜６の整数である）

(In the formula, R ⁷ and R ⁸ each represent a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond, and R ⁹ represents a hydrogen atom or 1 carbon atom. represents a hydrocarbon residue of the to 10, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, a and b are each an integer of 0 to 3 C is an integer of 1 to 4 satisfying 4-ab, n is an integer of 0 to 2, and p is an integer of 1 to 6)

  Examples of the silane compound represented by the structural formula (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxy Ethyldimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxypro Le trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

Examples of the silane compound represented by the structural formula (6) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane. Can be mentioned.
Examples of the silane compound represented by the structural formula (7) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxyethyldimethoxy. Examples include methylsilane and γ-methacryloyloxypropyltrimethoxysilane.
Examples of the silane compound represented by the structural formula (8) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

Examples of the silane compound represented by the structural formula (9) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like.
Examples of the silane compound represented by the structural formula (10) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.
Such a silane compound is preferably used in a proportion of 0 to 3 mole parts relative to 1 mole part of the solid content of the inorganic fine particles (a-3). When the usage-amount of a silane compound exceeds 3 mol part, the abrasion resistance of the photocurable sheet obtained may fall. The inorganic fine particles surface-treated with the silane compound can be obtained by heating and stirring the silane compound and the inorganic fine particles in the presence of a small amount of water.

As a method of adding the inorganic fine particles (a-3) to the thermoplastic resin (a-1), a method of previously synthesizing the thermoplastic resin (a-1) in a solvent and mixing the inorganic fine particles, Moreover, arbitrary methods, such as the method of superposing | polymerizing a thermoplastic resin (a-1) on the conditions which mixed the vinyl polymerizable monomer and inorganic fine particle which comprise a thermoplastic resin (a-1), can be selected. .
In the present invention, when the photopolymerizable functional group in the thermoplastic resin (a-1) having a photopolymerizable functional group in the side chain is an alicyclic epoxy group, the alicyclic epoxy group and the surface of the inorganic fine particles Functional groups (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 contain 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.
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. 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 the photocurable resin composition (A), in addition to the thermoplastic resin (a-1), the photopolymerization initiator (a-2), and the inorganic fine particles (a-3), a sensitizer, 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, it is preferable that substantially no crosslinkable monomer or oligomer that is liquid at 40 ° C. or low molecular weight crosslinkable monomer or oligomer having a molecular weight of 2,000 or less is contained. If such a liquid or molecular weight of 2,000 or less crosslinkable monomer or oligomer is contained, it will have surface adhesiveness during long-term storage or thermoforming, causing problems in the printing process or insert molding. In some cases, the mold may be contaminated during in-mold molding. It is more preferable that the liquid crosslinkable monomer and oligomer are not substantially contained at 50 ° C., and it is more preferable that the liquid crosslinkable monomer and oligomer are not substantially contained at 60 ° C.
In the present invention, since the photocurable resin composition (A) as described above is used, when the photocurable sheet is formed by laminating the photocurable resin composition on the base sheet (B). However, 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.

  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 There is a method of 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., and performing heat drying for removing the solvent (S) to obtain a laminated sheet.

  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. A volatile solvent that does not have a significant adverse effect and has a boiling point of + 80 ° C. or lower, preferably + 30 ° C. or lower, from the glass transition temperature of the acrylic resin other than the crosslinked rubber component in the base sheet (B). There is no particular limitation. 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 Various solvents such as a solvent having two or more kinds of functional groups such as ethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, and morpholine can be used.

The base sheet (B) is a thermoplastic acrylic resin sheet composed of two or more acrylic resin layers having different thermal deformation temperatures. The thermal deformation temperature of the layer in contact with the photocurable resin composition (A) layer is ASTM D648. It is necessary to be less than 85 ° C. in the measurement based on it.
When the heat distortion temperature is less than 85 ° C., the adhesion between the layer of the photocurable resin composition (A) and the base sheet is good.
Moreover, it is preferable that the thermal deformation temperature of the acrylic resin layer which contacts a photocurable resin composition (A) layer is 50 degreeC or more. When the heat distortion temperature is 50 ° C. or higher, not only is there a possibility that deformation such as elongation occurs in the base sheet when the base sheet is heated and dried after coating the layer of the photocurable resin composition. For example, there is no risk of damaging the appearance when used in applications where the surface layer may be heated by sunlight, such as the exterior or interior of a vehicle.

  The thermal deformation temperature of the acrylic resin layer other than the acrylic resin layer in contact with the photocurable resin composition (A) layer is preferably 85 ° C. or higher. When the heat distortion temperature is 85 ° C. or higher, not only the surface hardness of the photocurable sheet is good, but also the drying temperature can be increased within a range in which deformation such as elongation does not occur in the base sheet. It can be efficiently dried with the drying equipment. If the drying temperature can be further increased, the amount of the remaining organic solvent in the photocurable resin composition (A) layer can be reduced, so that the curability is poor (scratch resistance, chemical resistance, weather resistance is poor). Various problems caused by the residual solvent, such as poor storage stability, and the like. 90 degreeC or more is more preferable.

As a manufacturing method of the base material sheet (B) which consists of an acrylic resin layer from which two or more layers differ in heat-deformation temperature, it can manufacture by laminating | stacking an acrylic resin layer by the following methods.
A method of laminating each acrylic resin layer after forming it into a sheet, a method of laminating another acrylic resin layer simultaneously on the acrylic resin layer formed into a sheet while melting and extruding, and laminating each acrylic resin layer simultaneously while melting and extruding The method, the method of apply | coating and laminating | stacking another acrylic resin on the acrylic resin layer shape | molded in the sheet form, or the method of casting polymerizing another acrylic resin on the formed acrylic resin layer, etc. are mentioned. .

Examples of a method of laminating each acrylic resin layer after forming it into a sheet include laminating methods such as laminating by dry lamination, wet lamination, hot melt lamination, and the like. If heat fusion is possible, lamination can be performed by a hot press laminating method.
Examples of a method for simultaneously laminating another acrylic resin layer while being melt-extruded on an acrylic resin layer previously formed into a sheet shape include a laminating method such as an extrusion laminating method for laminating while melt-extruding into a sheet shape with a T die or the like.
As a method of laminating each acrylic resin layer at the same time while melt extrusion, a laminating method by coextrusion molding can be mentioned. Examples of the die shape in co-extrusion include a T-die method and an inflation method using a circular die. Examples of the lamination method in coextrusion molding include a lamination method such as a method of bonding inside a die by a feed block method or a multi-manifold method, and a method of bonding a plurality of die lips to one die and bonding them outside the die.

As a method of applying and laminating another acrylic resin on the acrylic resin layer formed into a sheet shape, a solution obtained by dissolving an acrylic resin in a solvent such as an organic solvent, gravure printing method, screen printing method, offset printing method, etc. Known printing methods, blade coating method, rod coating method, roll doctor coating method, knife coating method, comma coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, dip coating method There is a method in which coating is performed on a sheet formed in advance by a known coating method such as, and then drying by heating for solvent removal and laminating.
As a method of casting polymerization of another acrylic resin on the formed acrylic resin layer and laminating, the casting polymerization is performed after pasting the acrylic resin formed into a film on the inner wall surface of the casting polymerization mold. And a method of performing cast polymerization after an acrylic resin is coated on the inner wall surface of a mold for cast polymerization.
Among these, the lamination method by coextrusion molding by the T-die method is preferable from an economical point.

  Prior to lamination, when the acrylic resin layer is previously formed into a sheet shape, it can be produced by various known sheet forming methods such as a casting polymerization method, a T-die method, and a calendar method. Examples of the casting polymerization method include a method in which a raw material is injected into a space formed by a gasket such as a soft vinyl chloride resin and a pair of molds, polymerized and cured, and the polymer is peeled off from the mold and taken out. Examples of the members constituting the pair of molds include a glass plate, a chrome plated plate, a stainless plate, and the like. The opposing surfaces of a pair of endless belts that face each other at a predetermined interval are used as a pair of molds, and the raw material is injected into a space formed by the two gaskets and the molds that run following the travel of the endless belts. The plate-like polymer can be peeled off from the endless belt which is a mold by polymerization and curing.

In addition, prior to lamination, when the acrylic resin layer is previously formed into a film shape, the acrylic resin composition is not limited to the T-die method, other melt extrusion methods such as an inflation method, calendar method, melt casting method, etc. It can also be produced by various known film forming methods. In view of economy, the method using the T-die method is particularly preferable.
In the T-die method, it is preferable to form a film so that the substrate sheet cooled by the cooling roll comes into contact with the cooling roll again. In this way, dirt generated on the cooling roll can be removed continuously, so that the cooling roll is always kept clean and the appearance of the base sheet can be kept good. On the other hand, when a film is formed in such a way that the base sheet is in contact with the cooling roll only once, dirt accumulates on the cooling roll over time, and at a certain point, it is transferred to the base sheet to cause a large appearance defect. It becomes.
When forming a base sheet by the T-die method, the surface smoothness of the resulting base sheet can be improved by using a method of forming a film by sandwiching it between a plurality of metal rolls, non-metal rolls and / or metal belts. In addition, it is possible to suppress printing omission when printing is performed on the base sheet.

  Examples of the metal roll include a mirror touch roll made of metal, and a roll used in a sleeve touch system composed of a metal sleeve (metal thin-film pipe) and a molding roll (see, for example, Japanese Patent No. 2808251 and WO 97/28950). ) And the like. Moreover, examples of the non-metallic roll include a touch roll made of silicon rubber or the like. Furthermore, examples of the metal belt include a metal endless belt. A combination of a plurality of these metal rolls, non-metal rolls and metal belts can also be used (for example, JP 2002-301754 A, JP 2002-301755 A, JP 10-279766 A, Open 2003-25412 gazette, special table 2001-525277 gazette).

In the above-described method for forming a film by sandwiching a plurality of metal rolls, non-metal rolls and / or metal belts, the acrylic resin composition after melt extrusion is substantially free of banks (resin pools). It is preferable to form a film by holding the film and transferring the surface without substantially rolling.
When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is surface-transferred without rolling, so the heat shrinkage rate of the base sheet formed by this method is It can also be reduced.
In addition, when forming a film using a plurality of metal rolls, non-metal rolls and / or metal belts, the surface of at least one metal roll, non-metal roll or metal belt used is embossed, matted, etc. By applying the shape processing, the shape can be transferred to one side or both sides of the base sheet.

  The thickness of the base sheet is preferably 500 μm or less, and more preferably 100 to 500 μm. When the thickness is 100 μm or more, a sufficient depth can be obtained as the appearance of the molded product, and a sufficient thickness can be maintained even when the molded product is stretched particularly in a complicated shape. The upper limit of these ranges is that the rigidity is moderately suppressed to maintain good laminating properties and secondary workability, the mass per unit area is suppressed to maintain economy, and the acrylic resin composition is made into a sheet. This is significant in terms of improving the film-forming property when formed into a shape and stably producing a substrate sheet.

Moreover, although the thickness of each acrylic resin layer of the base material sheet (B) which consists of an acrylic resin layer from which two or more heat deformation temperatures differ is not specifically limited, the acrylic resin which contact | connects a photocurable resin composition (A) layer About a layer, 25 micrometers or less are preferable and 12 micrometers or less are more preferable. Adhesiveness with a photocurable resin composition (A) layer is enough that it is 25 micrometers or less, and hardness is also favorable. Although it does not specifically limit about acrylic resin layers other than the acrylic resin layer which contacts a photocurable resin composition (A) layer, It contacts a photocurable resin composition (A) layer from the thickness of the whole base material sheet (B). The remaining amount excluding the thickness of the acrylic resin layer corresponds to the thickness of these layers.
In order to form a coating film with sufficient thickness on a molded product by painting, it is necessary to apply several dozen times, which is costly and extremely deteriorated in productivity, as described above. In the case of a laminated molded product having a photocurable sheet using a base sheet as the outermost layer, the base sheet itself becomes a coating film, so that a very thick coating film can be easily formed, which is industrially advantageous. is there.

Each acrylic resin layer constituting the base sheet (B) may contain a crosslinked rubber-containing polymer as necessary. By including the crosslinked rubber-containing polymer, the impact resistance of each acrylic resin layer constituting the base sheet (B) can be improved. In the photocurable sheet of the present invention, cracks are produced during production and handling. It is difficult to cause destruction. Examples of the acrylic resin composition containing the crosslinked rubber-containing polymer include acrylic resin compositions as exemplified in JP-B-62-19309, JP-A-63-77963, and the like.
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 the photocurable resin composition (A) layer is laminated on the base sheet (B), and not only has excellent workability during insert molding and in-mold molding, It is a photocurable sheet capable of providing an insert molded product or an in-mold molded product having various physical properties (particularly weather resistance-surface hardness (abrasion resistance, pencil hardness) -adhesive 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, as the photocurable resin composition having one or more layers to be newly introduced, when a composition equivalent to or similar to the photocurable resin composition (A) is used, the surface of the photocurable sheet after photocuring is used. The properties (particularly adhesion, weather resistance, appearance, and design) tend to be favorable, which is preferable.
The photocurable sheet of the present invention obtained by the above method can also be used as 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, yellow pigments as azo pigments such as polyazo, isoindolinone and other organic pigments and inorganic pigments such as yellow lead, red pigments as azo pigments such as polyazo, quinacridone and other organic pigments and petals An inorganic pigment such as phthalocyanine blue or an inorganic pigment such as cobalt blue, an organic pigment such as aniline black as a black pigment, and an inorganic pigment such as titanium dioxide as a white pigment 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.

Further, 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 vapor deposition 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 thereof. It can be formed by a method such as a vacuum deposition method, a sputtering method, an ion plating method, or 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 during 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 decorating 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 30-750 micrometers. When the sheet thickness is less than 30 μm, the sheet thickness on the curved surface is remarkably lowered when deep drawing is performed, and as a result, 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. In addition, when the molding resin is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide resin having affinity with these resins Etc. 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. 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. In addition, the presence of the primer sheet provides an advantage that the surface defects of the injection molded product are minimized on the photocurable resin composition. In that case, the primer sheet needs to have a thickness sufficient to absorb surface defects of the molded resin while exhibiting a completely smooth upper surface of the photocurable resin composition.

Moreover, the photocurable sheet | seat of this invention can also provide a cover film further 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.
The cover film adheres to the photocurable resin composition (A) layer until insert molding or in-mold molding, as will be described later, and is immediately peeled when insert molding or in-mold molding is performed. It is necessary for the resin composition (A) layer to have appropriate adhesion and good releasability. 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.

  By the way, when the size of a molded product such as an automobile body panel or spoiler is large and the thickness of the molded product is thin, gas generated from the molded resin may remain in the molded resin, The air may easily intervene between the molding resin and the sheet, resulting in a problem that the adhesion of the sheet to the molding resin is lowered. In such a case, the problem can be solved by providing a gas-permeable layer on the sheet surface in contact with the molding resin. Examples of such a gas-permeable layer include woven fabrics and nonwoven fabrics composed of spandex, acrylic fibers, polyethylene fibers, polyamide fibers, and the like. Moreover, you may use what consists of a foamed layer instead of a woven fabric / nonwoven fabric. Examples of the method for forming the foamed layer include a method in which a resin solution containing a known foaming agent is applied and then foamed by heating or the like to form continuous pores.

  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.
The photocurable sheet or the photocurable decorative sheet is inserted and disposed 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) The side is 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. Especially when using a long sheet with a printing layer or vapor deposition layer for decoration, use a feeding device with a positioning mechanism so that the registration of the layer for decoration and the mold match. Good. In addition, when the sheet is intermittently fed, if the sheet is fixed after detecting the position of the sheet with the sensor, the sheet can always be fixed at the same position, and the positional deviation of the layer for decoration can be prevented. This is convenient because it does not occur.

Moreover, a photocurable sheet or a photocurable decorating sheet is preformed as needed. 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, a sheet can be formed 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. May be preformed into 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 in advance 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. So productivity is improved. 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 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 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 to approximate the shrinkage rate after molding of the molding resin to the shrinkage rate of the sheet because problems such as warping of the molded product and peeling of the sheet can be solved.
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 and punching the sheet by press working, a method of removing the sheet by manually tearing it off, etc. It can be carried out.
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 influence on the environment can be reduced as compared with conventional spray coating after molding. In particular, the photocurable sheet of the present invention has excellent workability and storage stability, no surface tackiness, good adhesion between the photocurable resin composition layer and the substrate sheet, and excellent surface hardness. The industrial utility value is extremely high.

Next, the present invention will be described in more detail based on examples. In the examples, “part” means “part by mass”. Abbreviations in the examples are as follows.
Methyl methacrylate MMA
Methyl acrylate MA
Ethyl acrylate EA
Butyl acrylate BA
Styrene St
Allyl methacrylate AMA
1,3-butylene glycol dimethacrylate 1,3BD
t-Butyl hydroperoxide tBH
Cumene hydroperoxide CHP

n-octyl mercaptan nOM
Methyl ethyl ketone MEK
Glycidyl methacrylate GMA
Azobisisobutyronitrile AIBN
Hydroquinone monomethyl ether MEHQ
Triphenylphosphine TPP
Acrylic acid AA
Sodium mono-n-dodecyloxytetraoxyethylene phosphate [trade name Phosphanol RS-610NA, manufactured by Toho Chemical Co., Ltd.] Emulsifier (1)
Lauryl peroxide LPO
2-hydroxyethyl methacrylate HEMA

[Synthesis Example 1] Synthesis of acrylic resin A having a photopolymerizable functional group in the side chain (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 was 99.5% or more, the polymer solid content was about 46% by weight, the number average molecular weight was about 25,000, the glass transition temperature was about 32 ° C., and the double bond equivalent was an average of 216 g / mol. .

[Synthesis Example 2] Synthesis of acrylic resin B having a photopolymerizable functional group in the side chain (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 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 is about 73 ° C., the alicyclic epoxy equivalent (side chain alicyclic epoxy). The average molecular weight per group) was 196 g / mol on average.

[Synthesis Example 3] Synthesis of acrylic resin C having photopolymerizable functional group in side chain (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 MMA 79.9 parts, GMA 20.1 parts and AIBN 0.5 parts 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 is 99.5% or more, the polymer solid content is about 35% by mass, the number average molecular weight is about 30,000, the glass transition temperature is about 105 ° C., and the double bond equivalent is an average of 788 g / mol. there were.

注）数値は固形分換算のモル部である。
１）ＩＰＡ−ＳＴ：イソプロパノール分散コロイダルシリカゾル（日産化学工業（株）製），シリカ粒子径＝１５ｎｍ
２）ＫＢＭ５０３：γ−メタクリロイルオキシプロピルトリメトキシシラン（信越化学工業（株）製），分子量＝２４８
攪拌機、コンデンサー及び温度計を備えたフラスコに、上記表２に記載の成分を入れ、攪拌しながら湯浴の温度を７５℃に上げ、その温度で２時間反応させることにより、イソプロパノール中に分散され、表面がシラン化合物で処理されたコロイダルシリカを得た。続いて、イソプロパノールを留去した後にトルエンを添加することを繰り返し、完全にイソプロパノールをトルエンに置換することにより、トルエン中に分散され、表面がシラン化合物で処理されたコロイダルシリカＳ１を得た。 [Preparation of surface-treated colloidal silica S1]

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 diameter = 15 nm
2) KBM503: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248
Into a flask equipped with a stirrer, a condenser and a thermometer, the components listed in Table 2 above were added, and the temperature of the hot water bath was raised to 75 ° C. while stirring, and the mixture was allowed to react at that temperature for 2 hours. Thus, colloidal silica whose surface was treated with a silane compound was obtained. Then, after adding isopropanol after distilling off isopropanol, the colloidal silica S1 disperse | distributed in toluene and the surface was processed with the silane compound was obtained by substituting toluene completely with isopropanol.

注）数値は固形分換算の質量部である。
１）１−ヒドロキシシクロヘキシルフェニルケトン
２）トリフェニルスルホニウム６フッ化アンチモネート [Preparation of Photocurable Casting Liquid Compositions 1-3]
Photocurable cast liquid compositions 1 and 2 having the composition of Table 3 were prepared using the acrylic resins A to C having a photopolymerizable functional group in the side chain, the surface-treated colloidal silica S1, and the compounds of Table 3. .

Note) Numerical values are parts by mass in terms of solid content.
1) 1-hydroxycyclohexyl phenyl ketone 2) triphenylsulfonium hexafluoroantimonate

[Manufacture of substrate sheets (S1) to (S18)]
a) Production of crosslinked rubber-containing polymer (I) In a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, the temperature was raised to 80 ° C., (i) shown below was added, and stirring was performed. While performing, 1/15 of the mixture of the raw material (b) shown below (raw material of the first inner layer polymer (I-A1)) was charged and held for 15 minutes. Thereafter, the remaining raw material (b) was continuously added at an increase rate of 8% / hour of the monomer mixture with respect to water. Thereafter, it was held for 1 hour to obtain a latex of the first inner layer polymer (I-A1).
Subsequently, 0.6 parts of SFS was added to this latex and held for 15 minutes, while stirring at 80 ° C. under a nitrogen atmosphere, the following raw materials (c) (raw material of the second inner layer polymer (I-A2)) Was continuously added at a rate of 4% / hr increase in the monomer mixture with respect to water. After that, the latex of the inner layer polymer ((I-A1) + (I-A2)) was obtained by maintaining the polymer for 2 hours and polymerizing the second inner layer polymer (I-A2).
Next, 0.4 parts of SFS was added to this latex, and kept for 15 minutes. While stirring at 80 ° C. in a nitrogen atmosphere, the following raw materials (d) (raw materials for outermost layer polymer (IB)) were added. The monomer mixture was continuously added at an increase rate of 10% / hour with respect to water. Thereafter, the outermost layer polymer (IB) was polymerized by holding for 1 hour to obtain a multilayer structure polymer (I) latex. The average particle size of the polymer (I) was 0.28 μm. The latex of the multilayer structure polymer (I) was subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water and dried to obtain a multilayer structure polymer (I).

Raw material (I)
SFS 0.6 part Ferrous sulfate 0.00012 part EDTA 0.0003 part Raw material (b)
MMA 18.0 parts BA 20.0 parts St 2.0 parts AMA 0.15 parts BD 1.2 parts tBH 0.18 parts Emulsifier (1) 0.75 parts

Raw material (C)
BA 50.0 parts St 10.0 parts AMA 0.4 parts BD 0.14 parts tBH 0.2 parts Emulsifier (1) 0.6 parts Raw materials (d)
MMA 57.0 parts MA 3.0 parts nOM 0.3 parts tBH 0.06 parts

b) Synthesis of Crosslinked Rubber-Containing Polymer (II) After charging 8.5 parts of ion exchange water into a vessel equipped with a stirrer, 0.3 parts of MMA, 4.5 parts of BA, 1,3 BD of 0.2 parts, AMA 0.05 A first monomer mixture consisting of 0.025 parts of CHP was added and stirred and mixed. Next, 1.3 parts of emulsifier (1) was added to the vessel while stirring, and stirring was continued again for 20 minutes to prepare an emulsion (N-1). The average particle size of the dispersed phase in the obtained emulsion was 10 μm.
Next, 186.5 parts of ion exchange water is put into a reaction vessel equipped with a cooler, and the temperature is raised to 70 ° C. Further, 0.20 part of sodium formaldehyde sulfoxylate is added to 5 parts of ion exchange water, sulfuric acid. A mixture prepared by adding 0.0001 part of ferrous iron and 0.0003 part of EDTA was added all at once. Next, the emulsion (N-1) was dropped into the reaction vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to obtain the innermost polymer.
Subsequently, after adding a second monomer mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of 1,3BD, and 0.25 part of AMA together with 0.016 parts of CHP to the reaction vessel over 90 minutes, The reaction was continued for 60 minutes to obtain a two-layer crosslinked rubber elastic body containing a cross-linked elastic polymer.

Subsequently, a third monomer mixture of MMA 6.0 parts, 4.0 parts BA, 0.075 parts AMA, and 0.0125 parts CHP was dropped into the reaction vessel over 45 minutes, and then the reaction was continued for 60 minutes. An intermediate polymer was formed.
Next, after dropping a fourth monomer mixture consisting of 55.2 parts of MMA, 4.8 parts of BA, 0.19 part of nOM, and 0.08 part of tBH over 140 minutes, the reaction was continued for 60 minutes. The outermost layer polymer was formed to obtain a latex of a crosslinked rubber polymer (II) having a multilayer structure. The obtained latex had a mass average particle diameter of 0.12 μm.
The obtained latex of crosslinked rubber-containing polymer (II) is poured into an aqueous solution containing 3 parts of calcium acetate, salted out, washed with water, separated and recovered, and dried to form a powdered crosslinked rubber-containing polymer. (II) was obtained. The gel content of the crosslinked rubber-containing polymer (II) was 60%.

c) Production of thermoplastic polymer (III) 200 parts of ion-exchanged water substituted with nitrogen were charged in a reaction vessel, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of nOM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was held for 2 hours to complete the polymerization to obtain a latex of thermoplastic polymer (III). This latex was added to a 0.25% aqueous sulfuric acid solution to coagulate the polymer, and then dehydrated, washed with water and dried to recover the powdery thermoplastic polymer (III). The reduced viscosity of this thermoplastic polymer (III) was 0.38 liter / g.

d) Production of thermoplastic polymer (VIII) The following mixture was charged into a reaction vessel equipped with a stirrer, reflux condenser and nitrogen gas inlet.
MA 10 parts MMA 60 parts HEMA 30 parts nOM 0.15 parts LPO 0.5 parts MMA / methacrylate /
Copolymerization of ethyl methacrylate sulfonate 0.05 parts Sodium sulfate 0.5 parts Ion-exchanged water 250 parts The inside of the container is sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, in a nitrogen gas stream Polymerization proceeded. After 2 hours, the temperature was raised to 90 ° C. and maintained for an additional 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a hydroxyl group-containing acrylic polymer. The reduced viscosity of the hydroxyl group-containing acrylic polymer was 0.069 l / g, and the glass transition temperature was 77 ° C.

e) Production of Acrylic Sheet Using the crosslinked rubber-containing polymers (I) and (II) obtained as described above, the thermoplastic polymer shown in Table 4, and the compounds shown in Table 5, They were mixed with the Henschel mixer at the indicated ratio. Next, this mixture was melt-kneaded at a cylinder temperature of 230 ° C. using a degassing twin-screw extruder to obtain pellets of an acrylic resin composition.
Two acrylic resin compositions shown in Table 6 were coextruded at a cylinder temperature of 180 to 240 ° C. and a T die temperature of 240 ° C. using a 40 mmφ single screw extruder, a 65 mmφ single screw extruder, and a feed block die, and acrylic. Acrylic resin sheets (S1) to (S3), (S5), and (S7) having a total thickness of 125 μm in which the thickness of the first resin layer was 10 μm and the thickness of the second acrylic resin layer was 115 μm were obtained. The acrylic resin sheets (S14) to (S17) were obtained as a single layer with a thickness of 125 μm.

In addition, the two types of acrylic resin compositions shown in Table 6 were molded into a sheet of 115 μm in advance with a 65 mmφ single screw extruder, a cylinder temperature of 180 to 240 ° C., and a T die temperature of 240 ° C. Then, a first layer acrylic resin composition dissolved in toluene / MEK = 1: 1 at a solid content of 25% is applied by a bar coater to a dry thickness of 10 μm, and an acrylic resin having a total thickness of 125 μm Sheets (S4), (S6), and (S8) were obtained.
Further, as the acrylic resin composition F, a commercially available acrylic resin sheet (acrylite L (manufactured by Mitsubishi Rayon Co., Ltd.); trade name) having a thickness of 2 mm is used as the second layer, and the acrylic resin composition to be the first layer is toluene / MEK. = 1: 1 dissolved at a solid content of 25% was coated with a bar coater so that the dry thickness was 10 μm, and acrylic resin sheets (S9), (S10), and (S13) were obtained. Also, the two acrylic resin compositions shown in Table 6 were formed into a sheet of 10 μm in advance with the 65 mmφ single screw extruder, cylinder temperature 180-240 ° C., and T-die temperature 240 ° C. as the first layer. And it hot-press-laminated on the commercially available acrylic resin sheet of thickness 2mm used as an acrylic resin composition used as a 2nd layer, and obtained the acrylic resin sheet (S11). The acrylic resin sheet (S18) was the above-mentioned commercially available acrylic resin sheet itself having a thickness of 2 mm.

  100 parts of MMA was supplied to a polymerization kettle equipped with a condenser, a thermometer and a stirrer, and the pressure was reduced at −90 kPa for 10 minutes while stirring. Next, the pressure is returned to atmospheric pressure with nitrogen gas, heating is started, and when the internal temperature reaches 60 ° C., 2,2′-azobis- (2,4-dimethylvaleronitrile), which is a radical polymerization initiator, is obtained. 05 parts were added, and further heated to an internal temperature of 100 ° C. and held for 8 minutes. Thereafter, the mixture was cooled to room temperature by cooling under reduced pressure, and 0.002 part of 2,4-dimethyl-6-t-butylphenol as a polymerization inhibitor was added to obtain acrylic syrup. The polymerization rate of the acrylic syrup was about 20%, and the viscosity was 1.5 Pa · s. To 100 parts of this acrylic syrup, 0.3 part of t-hexylperoxypivalate as a radical polymerization initiator was added, stirred, and degassed under reduced pressure at -90 kPa for 5 minutes. This acrylic syrup was poured into a mold, which was two tempered glass plates having a size of 300 × 300 × 6 mm laminated at intervals of about 3 mm through a polyvinyl chloride gasket and fixed by a clamp. Prior to the mold assembly, an acrylic film was adhered to one surface of the tempered glass plate using MMA as an adhesion liquid, and then assembled so that the film adhesion surface faced inward. Next, the mold into which this syrup was injected was immersed in warm water at 82 ° C. for 30 minutes to be polymerized and cured, further heat-treated in an air heating furnace at 130 ° C. for 1 hour, cooled to 90 ° C., and then cured in the mold. The product (this acrylic syrup cured product is referred to as acrylic resin composition G) was peeled off to obtain an acrylic resin sheet (S12) having a plate thickness of about 2 mm.

In addition, various physical properties were measured by the following test methods about the obtained thermoplastic polymer and sheet.
(1) Reduced viscosity of thermoplastic polymer 0.1 g of the polymer was dissolved in 100 ml of chloroform and measured at 25 ° C.
(2) Thermal deformation temperature of sheet composition Pellets of the sheet composition were molded by injection molding into a thermal deformation temperature measurement specimen based on ASTM D648, annealed at 80 ° C for 24 hours, and then subjected to low load (4.6 kg / cm ² ) in accordance with ASTM D648.

[Example 1]
The photocurable cast liquid composition 1 is stirred with a propeller mixer, and applied to the first layer side on the base sheet (S1) produced by the above method with a comma roll coater with a coating width of 200 mm. It was.
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 7 below is suitable for the movement of the sheet. The solvent was volatilized by passing it through a method in which hot air was fed so as to form a flow) at a speed of 5 m / min to form a photocurable resin layer having a thickness of 8 μm. Table 7 shows the residence time of each drying zone at this time.

Subsequently, it was slit into a width of 150 mm and wound up in a roll shape around an ABS core to a length of 20 m.
These photocurable sheets are placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, and then the sheet is preheated with an infrared heater (temperature 350 ° C.) for 10 seconds, and further The sheet was made to follow the mold shape by vacuum suction while 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 8.
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 8, the adhesion between the layer of the photocurable resin composition and the base sheet was good, and no peripheral peeling or cross-cutting peeling was observed even after the peel test. In addition, other surface properties were good.
Further, after being stored in a roll state at room temperature for about 2 weeks, the adhesiveness of the surface was evaluated while winding. The results are shown in Table 8.

[Sheet property evaluation method]
a) Pencil hardness test:
In accordance with JIS K 5400, evaluation was performed using Uni (Mitsubishi Pencil Co., Ltd .; trade name) as a pencil.
b) 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 the appearance of the film was peeled off at an angle of 90 ° after press-bonding Nichiban cello tape (cross-cut 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

c) 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 d) Warm water resistance:
The sheet state after being immersed in warm water at 40 ° C. for 24 hours was visually evaluated.
○: Good △: Thin whitening ×: Remarkable whitening

e) Transparency:
In accordance with ASTM D1003, the total light transmittance and haze were measured using a haze meter.
f) Abrasion resistance:
The haze value was measured with a haze meter after a Taber abrasion test (the test was carried out at a load of 500 g on one side, a CS-10F abrasion wheel, a rotational speed of 60 rpm, and the number of tests of 100). And the numerical value represented by (the haze value after the test) − (the haze value before the test) was shown as wear resistance (%).
g) 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 2000 hours in a cycle of 48 minutes for drying and 12 minutes for rain.
○: Good ×: Whitening or cracking

[Examples 2 to 10]
A photocurable sheet was produced in the same manner as in Example 1 except that the photocurable cast liquid composition 1 and the base sheet (S1) of Example 1 were changed to the combinations shown in Table 8, and in-mold A molded product was obtained. The results are shown in Table 8.

[Examples 11 to 15]
The photocurable casting liquid composition 1 and the base sheet (S1) of Example 1 were changed to the combinations shown in Table 8. In addition, it applied so that dry thickness might be set to 10 micrometers with the bar coater, and manufactured the photocurable sheet | seat. Next, using a vacuum forming machine equipped with a cylindrical mold (diameter 100 mm, depth 20 mm), vacuum forming was performed under conditions of a mold temperature of 60 ° C. and a sheet temperature of 170 ° C. to obtain a vacuum formed product. In addition, it installed in the direction where the layer of a photocurable resin composition contacts a metal mold | die, and the stain | pollution | contamination of the metal mold | die at this time was evaluated visually. The evaluation given in Example 1 was performed on the vacuum formed product. The results are shown in Table 9.

[Comparative Examples 1-3]
Except for the photocurable cast liquid composition 3 in place of the photocurable cast liquid composition 1 of Example 1 and the base sheet shown in Table 8 instead of the base sheet (S1), all the examples In-mold molded product was obtained in the same manner as in Example 1. Although the surface properties of the obtained molded article were good, in Comparative Examples 1 and 2, peeling was slightly observed when the peeling test was repeated 5 times. In Comparative Example 3, the photocurable resin composition after the peeling test was observed. Adhesion between the layer and the substrate sheet was poor, and remarkable peeling around the grid and peeling of the grid were observed. The results are shown in Table 8.

[Comparative Example 4]
Except for using the photocurable cast liquid composition 3 instead of the photocurable cast liquid composition 1 of Example 1 and the base sheet (S7) instead of the base sheet (S1), all are the same as in Example 1. Thus, an in-mold molded product was obtained. The surface properties of the obtained molded product and the adhesion between the layer of the photocurable resin composition after the peel test and the base sheet are good, but the surface hardness is remarkably inferior. The results are shown in Table 8.

[Comparative Example 5]
The photocurable casting liquid composition 1 and the base sheet (S1) of Example 1 were changed to the combinations shown in Table 8. In addition, it applied so that dry thickness might be set to 10 micrometers with the bar coater, and manufactured the photocurable sheet | seat. Next, using a vacuum forming machine equipped with a cylindrical mold (diameter 100 mm, depth 20 mm), vacuum forming was performed under conditions of a mold temperature of 60 ° C. and a sheet temperature of 170 ° C. to obtain a vacuum formed product. In addition, it installed in the direction where the layer of a photocurable resin composition contacts a metal mold | die, and the stain | pollution | contamination of the metal mold | die at this time was evaluated visually. The evaluation given in Example 1 was performed on the vacuum formed product. The adhesion between the layer of the photocurable resin composition after the peel test and the substrate sheet was poor, and remarkable peeling around the grid and peeling of the grid were observed. The results are shown in Table 9.

[Examples 16 to 25]
In the same manner as in Examples 1 to 10, a photocurable sheet having a photocurable resin layer having a thickness of 10 μm on each base sheet 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. Since these sheets have no surface tackiness, printability was good.
After these photocurable decorative sheets are placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, the sheet is preheated for 15 seconds with an infrared heater (temperature of 300 ° C.). Further, the sheet was made 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, using a UV irradiation device, the photocurable resin composition is cured by irradiating with UV rays of about 700 mJ / cm ² , and has a high surface hardness, excellent gloss, and has a printed pattern and excellent design. I got a product.

[Examples 26 to 35]
In the same manner as in Examples 1 to 10, photocurable sheets having a photocurable resin layer having a thickness of 10 μm on each base sheet were 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. Since these sheets have no surface tackiness, printability was good.
Furthermore, after forming the contact bonding 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 placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, the sheet is preheated for 15 seconds with an infrared heater (temperature of 300 ° C.). Further, the sheet was made 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.

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 materials such as headlamp covers, taillight covers, windshield parts, etc., automotive interior materials such as instrument panels, console boxes, meter covers, door lock bezels, steering wheels, power window switch bases, center clusters, dashboards, etc. Applications for front panels, buttons, emblems, surface cosmetics, etc. for AV equipment and home appliances, applications for housings for mobile phones, display windows, buttons, etc., and furniture exterior materials Building interior materials such as walls, ceilings and floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, fittings such as window frames, doors, handrails, sills and duck Surface cosmetic materials, various displays, lenses, mirrors, goggles, window glass, reflectors, and other optical components, or interior / exterior materials for various vehicles other than automobiles such as trains, aircraft, and ships, bottles, cosmetics Various packaging containers and materials such as containers and accessory cases, and various other uses such as miscellaneous goods such as prizes and accessories can be suitably used. 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 of painting the surface of the molded product, the productivity is good, and the influence on the environment is small.

Claims (13)

  Photocuring comprising a layer of a photocurable resin composition (A) containing a thermoplastic resin (a-1) having a photopolymerizable functional group and a photopolymerization initiator (a-2), and a base sheet (B) Thermal deformation of a layer in contact with the photo-curable resin composition (A) layer, which is a thermoplastic acrylic resin sheet composed of acrylic resin layers having two or more layers having different thermal deformation temperatures. A photocurable sheet having a temperature of less than 85 ° C.   The photocurable sheet according to claim 1, wherein the thermoplastic resin (a-1) having a photopolymerizable functional group is an acrylic resin having a photopolymerizable functional group in the molecule.   The photocurable sheet according to claim 1, wherein the thermoplastic resin (a-1) having a photopolymerizable functional group is an acrylic resin having a photopolymerizable functional group in a side chain.   The photocurable sheet according to any one of claims 1 to 3, wherein the photocurable resin composition (A) does not substantially contain a crosslinkable compound other than (a-1).   The photocurable sheet according to any one of claims 1 to 4, wherein a thermal deformation temperature of an acrylic resin layer other than the acrylic resin layer in contact with the photocurable resin composition (A) layer is 85 ° C or higher.   The photocurable sheet according to any one of claims 1 to 5, wherein the photocurable resin composition (A) contains inorganic fine particles (a-3).   A step of coating the base sheet (B) with a photo-curable cast liquid composition comprising the photo-curable resin composition (A) and the solvent (S), and heating the base sheet (B) after coating. The photocuring according to any one of claims 1 to 6, comprising a layer of the photocurable resin composition (A) and a base sheet (B), comprising a step of volatilizing the solvent (S). Manufacturing method of adhesive sheet.   The photocurable additive which formed at least 1 layer or more among a printing layer, a vapor deposition layer, an adhesive layer, and a primer layer in the base-material sheet | seat (B) side of the photocurable sheet described in any one of Claims 1-6. Decorative sheet.   The photocurable sheet or photocurable decorative sheet according to any one of claims 1 to 6 and claim 8 is inserted so that the photocurable resin composition (A) side faces the inner wall surface of the mold. Step of placing, closing the mold, injecting molten resin into the mold, and solidifying the resin, thereby forming a resin molded product having a photocurable sheet or photocurable decorative sheet arranged on the surface And the manufacturing method of the molded article including the process of photocuring the photocurable resin composition of the molded article surface by irradiating with light.   The photocurable sheet or photocurable decorative sheet according to any one of claims 1 to 6 and claim 8 is inserted so that the photocurable resin composition (A) side faces the inner wall surface of the mold. The step of placing, the step of preforming the photocurable sheet or the photocurable decorative sheet and causing the sheet to follow the mold shape, the mold is closed, the molten resin is injected into the mold, and the resin is solidified A step of forming a resin molded product having a photocurable sheet or a photocurable decorative sheet disposed on the surface thereof, and a step of photocuring the photocurable resin composition on the surface of the molded product by light irradiation. Manufacturing method of molded products.   The photocurable sheet or photocurable decorative sheet according to any one of claims 1 to 6 and claim 8 is preliminarily placed so that the photocurable resin composition (A) side faces the inner wall surface of the mold. A step of inserting and arranging in a molding die, 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 The step of inserting and placing the resin in the molding die so that the photocurable resin 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 Molding comprising a step of forming a resin molded product having a photocurable sheet or a photocurable decorative sheet disposed on the surface thereof, and a step of photocuring the photocurable resin composition on the surface of the molded product by light irradiation. Product manufacturing method.   The molded article which has the photocurable sheet or photocurable decorating sheet of any one of Claims 1-6 and Claim 8 in the outermost surface. The molded product obtained by the manufacturing method described in any one of Claims 9-12.