JP2003034002A - Photosetting sheet and method for manufacturing molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably provide a photosetting sheet advantageously usable for manufacturing a molded article having good design effect, excellent in abrasion resistance, weatherability and chemical resistance, having no surface tackiness and excellent in processability and storage stability. SOLUTION: The photosetting sheet includes a layer comprising a photosetting resin composition (A) and a substrate sheet (B). The photosetting resin composition (A) is represented by the formula (1): X=Y/[a/(a+b)] [wherein, X is the amount of a solvent in the photosetting sheet per a unit weight of the photosetting sheet, a is the thickness (μm) of the layer of the photosetting resin composition (A), b is the thickness (μm) of the substrate sheet (B) and Y is the amount of the solvent per a unit weight of the photosetting sheet] and the value of the amount (X) of the solvent of the photosetting resin composition (A) is not more than 10. A photosetting decorative sheet using the photosetting sheet, a photosetting insert molding sheet and a method for manufacturing a molded article using the molding sheet are also disclosed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable sheet and a method for producing a molded article using the same. The present invention particularly relates to a photocurable sheet having excellent appearance, designability, abrasion resistance, chemical resistance and weather resistance, and having no surface tackiness, and a method for producing a molded article using the same.

[0002]

2. Description of the Related Art As a method for decorating the surface of a plastic product at the same time as molding, (1) a method of forming a pattern on the inner surface of the mold in advance, (2) mounting a transfer film on the inner wall surface of the mold, A method of transferring the pattern of the film to the outer surface of the molded product at the same time as the molding, (3) A functional sheet or a printing sheet is attached to the inner wall surface of the mold, and the sheet is attached to the surface of the molded article at the same time as the molding Methods etc. have been proposed. Regarding the method (2) or (3), for example, JP-A-60-250925 and JP-B-59-3684.
No. 1 and Japanese Patent Publication No. 8-2550, a weather resistance imparting sheet or a printing sheet is formed on the inner wall surface of a mold, and then a molding resin is injection-molded to produce a molded product whose surface is covered with the sheet. The method of doing is proposed.

However, in the above-mentioned technique, since the decoration and the imparting of functionality are performed by the transfer of the thermoplastic sheet or the printing, the surface hardness of the obtained molded product is insufficient. For example, when imparting weather resistance to a molded product, 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 pre-crosslinked sheet having a high surface hardness must be used. However, such a sheet is difficult to apply to a three-dimensional molded article.

[0004]

Therefore, Japanese Patent Publication No. 7-3
No. 23, the photocurable resin layer formed of a resin composition containing an acrylic resin, a compound having a reactive vinyl group and a photopolymerization initiator, and a sheet substrate are laminated. Has been proposed. However, in this method, since the sheet before photocuring contains a compound having a low molecular weight reactive vinyl group, there is a phenomenon that the surface has tackiness or the tackiness of the surface changes with time. Occurs, and the storage stability in the roll state is poor. Specifically, there were problems such as sticking and unwinding, and compound exuding from both ends unless stored at low temperature. Furthermore, due to its surface tackiness, problems have occurred in the printing process when used as a printing sheet.

In order to solve such a problem, the present inventors first laminated a composition comprising an acrylic resin having an alicyclic epoxy group or a radically polymerizable unsaturated group in a side chain and a photopolymerization initiator. We proposed a photocurable sheet without surface tackiness by developing the above-mentioned base sheet. These photocurable sheets are photocurable sheets that have both excellent moldability before photocuring and excellent surface properties (hardness, weather resistance, etc.) after photocuring at a high level. The present inventors, through the process of developing these photocurable sheets, in order to stably obtain a photocurable sheet having good moldability and surface texture, the amount of solvent in the photocurable sheet, It was found that the amount of solvent in the photocurable resin composition, which is defined by the thickness of the photocurable resin composition layer and the thickness of the substrate sheet, needs to be a specific value or less, whereby the present invention can be obtained. Has been completed.

That is, the object of the present invention is to have excellent wear resistance, weather resistance and chemical resistance, which can be advantageously used for producing a molded article having a good design property, and has no surface tackiness. It is intended to stably provide a photocurable sheet having excellent processability and storage stability.

[0007]

In order to solve the above-mentioned problems, the present invention provides a photocurable sheet comprising a layer of a photocurable resin composition (A) and a base sheet (B), having the following formula: Provided is a photocurable sheet having a solvent amount (X) in the photocurable resin composition (A) represented by (1) of 10 or less.

X = Y / (a / (a + b)) (1) Here, X is the amount of solvent in the photocurable resin composition (A) per unit mass of the photocurable sheet, and a is photocurable. Is the film thickness (μ) of the resin composition (A) layer, b is the thickness (μ) of the base sheet (B), and Y is the amount of solvent per unit mass of the photocurable sheet.

The present invention also provides a photocurable sheet in which a cover film is temporarily attached to the photocurable resin composition (A) layer side.

The present invention also provides a photocurable decorative sheet including a printing layer and / or a vapor deposition layer formed on the base sheet side of the photocurable sheet.

The present invention further provides a photocurable decorative sheet including a printing layer and / or a vapor deposition layer formed on the base sheet side of the photocurable sheet, and an adhesive layer.

The present invention also provides a printing layer and / or a vapor deposition layer formed on the base sheet side of the photocurable sheet,
And a photocurable decorative sheet including an adhesive layer and a primer sheet.

The present invention also includes a step of inserting and placing the above-mentioned photocurable sheet or photocurable decorative sheet so that the photocurable resin composition (A) side faces the inner wall surface of the mold.
Closing the mold, injecting the molten resin into the mold, and solidifying the resin to form a photocurable sheet or a photocurable decorative sheet on the surface of which a resin molded product is formed, and light irradiation By doing so, a method for producing a molded article including a step of photocuring the photocurable resin composition on the surface of the molded article is provided.

The present invention further comprises the above-mentioned photocurable sheet or photocurable decorative sheet, which is a photocurable resin composition (A).
The step of inserting and arranging so that the side faces the inner wall surface of the mold, the step of preforming a photocurable sheet or a photocurable decorative sheet to make the sheet follow the shape of the mold, closing the mold, and melting the molten resin A step of forming a resin molded product with a photocurable sheet or a photocurable decorative sheet on the surface by injecting into a mold and solidifying the resin, and photocuring the surface of the molded product by irradiating light Provided is a method for producing a molded article, the method including the step of photocuring a resin composition.

The present invention further provides a method for producing a molded article, which further comprises the step of peeling and removing the cover film in advance in the method for producing a molded article.

The present invention also provides a molded article obtained by the above method.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be sequentially described below.

The photocurable sheet of the present invention is a photocurable sheet containing a layer of the photocurable resin composition (A) and a base sheet (B) and is represented by the following formula (1): The value of the solvent amount (X) in the curable resin composition (A) is 10 or less.

X = Y / (a / (a + b)) (1) Here, X is the amount of solvent in the photocurable resin composition (A) per unit mass of the photocurable sheet, and a is photocurable. Is the film thickness (μ) of the resin composition (A) layer, b is the thickness (μ) of the base sheet (B), and Y is the amount of solvent per unit mass of the photocurable sheet.

Thus, since the value of the solvent amount (X) in the photocurable resin composition (A) is as small as 10 or less, the photocurable sheet of the present invention has excellent physical properties (wear resistance). Properties, chemical resistance, non-surface tackiness, processability, storage stability, etc.) can be exhibited.

The photocurable resin composition (A) contains a compound which has two or more photopolymerizable functional groups in one molecule and which is cured by a photopolymerization reaction to form a crosslinked product. It is preferably a composition. As the photopolymerizable functional group of such a compound, a functional group having an ethylenically unsaturated group such as a vinyl group or a (meth) acrylic group, which reacts by a photoradical polymerization mechanism, or a photocation such as an alicyclic epoxy group. Examples thereof include functional groups that react by the polymerization mechanism.

When the photocurable resin composition (A) contains a low molecular weight crosslinkable compound, the surface of the photocurable sheet has tackiness and the storage stability of the sheet is lowered. It is preferable not to contain a crosslinking compound.

In particular, the photocurable resin composition (A) contains a thermoplastic resin (a-1) having a photopolymerizable functional group in its side chain, and substantially contains a crosslinkable compound other than (a-1). In the case of a constitution not specifically containing it, a photocurable sheet having remarkably good abrasion resistance, moldability and storage stability at the same time can be obtained, which is preferable. By introducing a structure having a photopolymerizable functional group in the polymer side chain in this way, the crosslinking reaction proceeds between the polymer side chains, so it is possible to achieve extremely good abrasion resistance without the inclusion of a low molecular weight crosslinkable compound. In addition to exhibiting the properties, there is an advantage that there is no tackiness on the sheet surface due to the absence of a low molecular weight crosslinkable compound, and the storage stability is excellent.

The photopolymerizable functional group may be any one capable of promoting polymerization upon irradiation with light.
A radically polymerizable unsaturated group or an alicyclic epoxy group represented by the following structural formula (1) is preferable.

[0025]

[Chemical 1]

The thermoplastic resin having a radically polymerizable unsaturated group in its side chain has, for example, a glass transition temperature of 25 to
Those having a radically polymerizable unsaturated group in the polymer at 175 ° C., preferably 30 to 150 ° C. are mentioned. Specifically, the following compounds (1) to (8) are used as the polymer.
In addition to a polymerized or copolymerized product of the above, a product in which a radically polymerizable unsaturated group is introduced by the methods (a) to (d) described below can be used.

(1) Monomer having hydroxyl group: N-methylol acrylamide, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
2-Hydroxy-3-phenoxypropyl (meth) acrylate, etc. (2) Carboxyl group-containing monomer: (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc. (3) Epoxy group-containing monomer: glycidyl ( (4) Aziridinyl group-containing monomer: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc. (5) Monomers having amino groups: (meth) acrylamide, diacetone acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. (6) Monomers having sulfone groups: 2-acrylamido-2-methyl Propanesulfonic acid, etc. (7) Isocyanate Monomers having: 2-isocyanatoethyl (meth), an addition product of a radical polymerizable monomer having diisocyanate and active hydrogen, such as an equimolar addition product of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate. Acrylate, etc. (8) Further, in order to adjust the glass transition temperature of the above-mentioned copolymer and to balance the physical properties of the photocurable sheet, the above-mentioned compound is copolymerized with a monomer copolymerizable therewith. You can also let it. Examples of such a copolymerizable monomer include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate and isobornyl (meth) acrylate, N.
-Phenylmaleimide, cyclohexylmaleimide, N
Examples thereof include imide derivatives such as butyl maleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene.

Next, a radically polymerizable unsaturated group is introduced into the polymer obtained as described above by the following methods (a) to (d).

(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 above-mentioned 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 above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction. Let

(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 or a monomer having an aziridinyl group, or a monomer having an isocyanate group Body or an equimolar addition product of a diisocyanate compound and a hydroxyl group-containing acrylic acid ester 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.

The thermoplastic resin having an alicyclic epoxy group in the side chain used in the present invention has, for example, a glass transition temperature of 25 to 175 ° C, preferably 30 to 150 ° C.
, Which have an alicyclic epoxy group in the polymer side chain. To give a concrete example of synthesis, for example, the first
As the method of (1), (meth) acrylate (9) having an alicyclic epoxy group is homopolymerized by a known polymerization method such as a solution polymerization method in the presence of a radical polymerization initiator, or (1) to (8) above. It can be obtained by copolymerizing with another copolymerizable monomer as shown in.

The thermoplastic resin having an alicyclic epoxy group in its side chain can be obtained by a method other than the above homopolymerization or copolymerization. For example, as a second method, a compound having an alicyclic epoxy group and a first reactive group,
It can be obtained by reacting a thermoplastic resin having a second reactive group that reacts with the first reactive group. As a typical example of the combination of the first reactive group and the second reactive group, there is a combination of an isocyanate group and a hydroxyl group as shown in Table 1 below.

[0036]

[Table 1]

In the above-mentioned first method, the (meth) acrylate (9) having an alicyclic epoxy group is not particularly limited as long as it can be copolymerized with another radically polymerizable monomer. Specifically, the following structural formula (2)
And a compound represented by

[0038]

[Chemical 2]

(In the above formula, R represents a methyl group or a hydrogen atom, and n is an integer of 0 to 5.) The amount of the photopolymerizable functional group in the side chain of the thermoplastic resin (a-1) is 2 Heavy bond equivalent (average molecular weight per side-chain radically polymerizable unsaturated group) or alicyclic epoxy equivalent (average molecular weight per side-chain alicyclic epoxy group) is the average calculated from the charged values. It is preferably 3000 g / mol or less from the viewpoint of improving scratch resistance and abrasion resistance. A more preferable range is 1200 g / mol or less on average,
The most preferable range is 600 g / mol or less on average.

As described above, by introducing a plurality of photopolymerizable functional groups involved in crosslinking into the thermoplastic resin, it is not necessary to use a low molecular weight crosslinking compound, and long-term storage or heat molding described later is performed. Even in some cases, it becomes possible to efficiently improve the cured physical properties without having surface tackiness.

The number average molecular weight of the thermoplastic resin (a-1) is preferably in the range of 5,000 to 2,500,000, more preferably 10,000 to 1,000,000. When the photocurable sheet formed using the photocurable resin composition (A) containing the thermoplastic resin (a-1) is insert-molded or in-molded, the mold releasability becomes good, and From the viewpoint of the surface hardness of the molded product after photocuring, the number average molecular weight is preferably 5,000 or more. On the other hand, from the viewpoint of easiness of synthesis and appearance, and the appearance of adhesion with the base sheet (B), the number average molecular weight is 2,
It is preferably 500,000 or less.

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

Considering the glass transition temperature of the obtained thermoplastic resin copolymer, it is preferable to use a vinyl polymerizable monomer having a high glass transition temperature as the homopolymer.

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

As will be described later, when the inorganic fine particles (a-3) are added to the photocurable resin composition (A) of the present invention, the functional groups (hydroxyl groups on the surface of the inorganic fine particles (a-3) (hydroxyl group) are added. Group, a carboxyl group, a silanol group, etc.), a vinyl having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a silyl halide group and an alkoxysilyl group in the molecule. The polymerizable monomer acts to further improve the physical properties such as rigidity, toughness and heat resistance of the obtained photocurable resin composition, and therefore, such a functional group is a radical polymerizable vinyl polymerizable monomer component. It may be contained as a part.

Examples of the vinyl polymerizable monomer containing such a reactive group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyl. Trichlorosilane, vinyltrimethoxysilane, γ- (meth)
Examples thereof include 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 a radical by light irradiation and a photocationic polymerization initiator that generates an acid. However, the photopolymerizable functional group of the side chain is radical polymerized. In the case of a polyunsaturated group, a photoradical polymerization initiator is used, and in the case of an alicyclic epoxy group, a photocationic polymerization initiator is used.

As the photo-radical polymerization initiator, known compounds can be used and are not particularly limited, but considering yellowing at the time of curing and deterioration at the time of weathering, acetophenone-based, benzophenone-based and acylphosphine oxide-based initiators can be used. An initiator which 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-trimethylpentylphosphine oxide and the like are preferable. Depending on the molding method, some of these may temporarily reach a temperature above the boiling point of the compound, so care must be taken. In order to increase the surface hardness of the molded product, an additive such as n-methyldiethanolamine that suppresses the inhibition of polymerization and curing 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 needs to be cured at 150 ° C. for about 30 seconds. Therefore, a peroxide having a low critical temperature such as lauroyl peroxide or t-butylperoxy-2 is used. -Ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.

The amount of the photoradical polymerization initiator added is preferably 5% by mass or less based on the compound having a photopolymerizable functional group in the side chain, since the residual amount after curing affects the weather resistance. 1% by mass or less is preferable for the amino-based photoradical polymerization initiator related to yellowing.

As the photocationic polymerization initiator, known compounds can be used and are not particularly limited, but specifically, diaryl iodonium salts, triaryl sulfonium salts, iron arene (aromatic hydrocarbon) complexes and the like can be used. Can be mentioned. Of these, a triarylsulfonium salt represented by the following structural formula (3) is more preferable in view of reactivity with a compound having an alicyclic epoxy group, coloring problems, and the like.

[0051]

[Chemical 3]

(In the above formula, R ¹ represents a substituted or unsubstituted aromatic ring through a carbon-carbon bond or a carbon-sulfur bond, and R ² and R ³ represent a substituted or unsubstituted aromatic ring, respectively. By selecting such a photo-cationic polymerization system, as compared with the photo-radical polymerization system, the curing shrinkage is small and the adhesiveness with the resin is excellent, so that the cured layer is less likely to crack or peel off. It may have advantages such as low odor before and after curing and no inhibition of polymerization by oxygen.

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 compound having a photopolymerizable functional group in the side chain.

The photocurable resin composition (A) contains inorganic fine particles (a) for the purpose of further improving scratch resistance and abrasion resistance.
-3) can be added. The inorganic fine particles (a-3) used in the present invention are not particularly limited in kind, particle diameter and morphology as long as the obtained photocurable resin composition is transparent. Examples of the inorganic fine particles include colloidal silica, alumina, titanium oxide, tin oxide, different element-doped tin oxide (ATO etc.), indium oxide, different element-doped indium oxide (ITO etc.), cadmium oxide, antimony oxide and the like. . These may be used alone or in combination of two or more. Among them, colloidal silica is particularly preferable from the viewpoints of availability and cost, and transparency and abrasion resistance of the obtained photocurable resin composition layer.

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

Examples of such organic solvents include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like. You can Above all, in order to disperse uniformly with the thermoplastic resin,
It is preferable to select an organic solvent capable of dissolving the thermoplastic resin.

The colloidal silica dispersed in an organic solvent is a commercial product dispersed in a dispersion medium, for example, methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene. Glycol silica sol E
G-ST, xylene / butanol silica sol XBA-S
T, 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 M
IBK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) can be used.

The particle size of the inorganic fine particles (a-3) is usually 2 from the viewpoint of transparency of the resulting photocurable resin composition layer.
It is preferably 00 nm or less. More preferably 10
It is 0 nm or less, and more preferably 50 nm or less.

The amount of the inorganic fine particles (a-3) added is 5 to 5 parts by mass of the inorganic fine particles based on 100 parts by mass of the solid content of the thermoplastic resin (a-1) having a photopolymerizable functional group in the side chain. 40
The range of 0 parts by mass is preferable, and the range of 10 to 200 parts by mass is particularly preferable. If the addition amount of the inorganic fine particles is less than 5 parts by mass, the abrasion resistance improving effect may not be observed, and if the addition amount exceeds 400 parts by mass, the photocurable resin composition (A In addition to the decrease in the storage stability of 1), the moldability of the obtained photocurable sheet may decrease.

In addition, the inorganic fine particles (a
As -3), those whose surface is previously treated with a silane compound represented by the following structural formula (4) may be used. Use of the 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 obtained 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 have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond. Optionally represents a hydrocarbon residue having 1 to 10 carbon atoms, R ⁶ represents a hydrogen atom, an ether bond, an ester bond, an epoxy bond, or a carbon-carbon double bond, which may have a carbon atom number of 1 to 10. Represents a hydrocarbon residue, a
And b are each an integer of 0 to 3, and c is 4-
Among the silane compounds represented by the structural formula (4), which is an integer of 1 to 4 that satisfies ab), the silane compounds represented by the following structural formulas (5) to (10) are preferred. Can be mentioned.

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)

[0063]

[Chemical 4]

(In the above formula, R ⁷ and R ⁸ are respectively
Represents a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond, R
⁹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and a and b are , Each is an integer of 0 to 3, and c is 4-a-
b is an integer of 1 to 4, n is an integer of 0 to 2, and p is an integer of 1 to 6) As the silane compound represented by the structural formula (5), for example, tetra Methoxysilane, tetraethoxysilane,
Tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyldimethoxysilane , Tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (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). Examples include silane.

Examples of the silane compound represented by the structural formula (7) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane and β-methacryloyl. Examples thereof include oxyethyldimethoxymethylsilane and γ-methacryloyloxypropyltrimethoxysilane.

Examples of the silane compound represented by the structural formula (8) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.

Examples of the silane compound represented by the structural formula (9) include γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.

Examples of the silane compound represented by the structural formula (10) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.

Such a silane compound is an inorganic fine particle (a-
It is preferable to use it in a ratio of 0 to 3 parts by mol with respect to 1 part by mol of the solid content of 3). When the amount of the silane compound used is more than 3 parts by mole, the abrasion resistance of the obtained photocurable sheet may decrease.

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) having a photopolymerizable functional group in the side chain, after the thermoplastic resin (a-1) is synthesized in advance, Inorganic fine particles may be mixed, or a thermoplastic resin (a-
Any method such as a method of polymerizing the thermoplastic resin under the condition that the vinyl polymerizable monomer constituting 1) and the inorganic fine particles are mixed 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, an alicyclic epoxy group and an inorganic group are used. Functional groups on the surface of fine particles (hydroxyl group, carboxyl group,
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 amine compounds 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 as not to remain excessively in the sheet.

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

The amount of at least one selected from ammonia and amine compounds having a boiling point of 100 ° C. or less is 100 parts by mass of solid content of the thermoplastic resin (a-1) having an alicyclic epoxy group in the side chain. 0.01 to 100 parts
It is preferably in the range of 0.5 parts by mass. From the viewpoint of maintaining the stability of the photocurable resin composition (A), the addition amount of at least one selected from ammonia and amine compounds having a boiling point of 100 ° C. or lower is preferably 0.01 parts by mass or more, but amine is preferable. When the amount of the compound added exceeds 0.5 parts by mass, even if the molded product obtained by insert molding or in-mold molding the photocurable sheet is photocured,
The cationic photopolymerization does not proceed and the scratch resistance and chemical resistance may be poor.

The photocurable resin composition (A) used in the present invention is required in addition to the thermoplastic resin (a-1), the photopolymerization initiator (a-2) and the inorganic fine particles (a-3). Depending on the case, additives such as a sensitizer, a modifying resin, a dye, a pigment, a leveling agent, an anti-repellent agent, an ultraviolet absorber, a light stabilizer and an oxidation stabilizer can be added.

The above-mentioned sensitizer accelerates the photo-curing reaction, and examples thereof include benzophenone, benzoin isopropyl ether and thioxanthone.

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

However, the photocurable resin composition (A) should not substantially contain a crosslinkable compound other than the thermoplastic resin (a-1). In particular, liquid crosslinkable monomers and oligomers at 40 ° C and low molecular weight crosslinkable monomers and oligomers having a molecular weight of 2000 or less should not be substantially contained. In particular, when a liquid crosslinkable monomer or oligomer at 40 ° C. or a low molecular weight crosslinkable monomer or oligomer having a molecular weight of 2000 or less is contained, it has surface tackiness during long-term storage or heat molding, and printing Problems may occur in the process, or the mold may be contaminated during insert molding or in-mold molding. More preferably, it should be substantially free of liquid crosslinkable monomers and oligomers at 50 ° C, and even more preferably substantially free of liquid crosslinkable monomers and oligomers at 60 ° C.

As the base material sheet (B) used in the present invention, a suitable material is selected depending on the method of use. For example, ABS (acrylonitrile / butadiene / styrene copolymer) type resin, AS (acrylonitrile / styrene copolymer) resin are used. Polymer resin, vinyl chloride resin, polystyrene resin, polyolefin resin such as polypropylene, fluorine resin, cellophane resin, cellulose resin, polyurethane resin, polyamide resin such as nylon, polyester resin, polycarbonate Examples of the sheet include a resin such as a resin, a polyvinyl alcohol resin, an ethylene vinyl alcohol resin, and a soft acrylic resin. Further, a composite body or a laminated body of each of these sheets can be used. Of these, a thermoplastic resin sheet having an elongation of 100% or more when heated at 100 ° C. is preferable because it can follow the mold shape well during insert molding or in-mold molding. Considering the adhesion with the photocurable resin composition (A), weather resistance, transparency, etc.,
More preferably, it is a thermoplastic acrylic resin sheet having a crosslinked rubber component. A transparent thermoplastic acrylic resin sheet having a crosslinked rubber component is disclosed in Japanese Patent Application Laid-Open No. 9-26361.
There is a transparent thermoplastic acrylic sheet obtained by extrusion-molding an acrylic resin having a multilayer structure as disclosed in Japanese Patent Laid-Open No. 4 and the like.

In the base material sheet (B), if necessary, a lubricant such as polyethylene wax or paraffin wax, a lubricant such as silica, spherical alumina or flake alumina, a benzotriazole type, or a benzophenone is used. system,
Ultraviolet absorbers such as fine particles of cerium oxide, light stabilizers such as hindered amine radical scavengers, plasticizers, stabilizers,
You may add various additives, such as a coloring agent.

Since the photocurable sheet of the present invention has the above-mentioned constitution, it has excellent moldability and storage stability before photocuring and excellent surface properties (hardness, weather resistance, etc.) after photocuring. It is a photo-curable sheet that is compatible with high dimensions. As will be described later, the photocurable sheet of the present invention is usually prepared by mixing a solution of the photocurable resin composition (A) in a solvent such as an organic solvent and dissolving the solution into a base sheet (B) by various coating methods. It is manufactured by coating the above and then drying for removing the solvent. At this time, if a large amount of the solvent remains in the photocurable sheet, the surface of the photocurable resin composition (A) layer before light irradiation becomes tacky, and the yield in the printing process decreases. In addition, problems such as deterioration of storage stability in a roll state and deterioration of mold contamination during insert molding or in-mold molding occur. Further, even if a molded product obtained by insert molding or in-mold molding of a photocurable sheet is photocured, surface properties such as scratch resistance, chemical resistance, and weather resistance may be poor. To solve such problems, the amount of solvent in the photocurable sheet, the amount of solvent in the photocurable resin composition defined by the thickness of the photocurable resin composition layer and the thickness of the substrate sheet It must be below a certain value.

Here, the value of the solvent amount (X) in the photocurable resin composition (A) is a numerical value represented by the above formula (1).

In the present invention, the amount of solvent (X) in the photocurable resin composition (A) can be measured by a method usually used for quantitative analysis of volatile substances. For example, it can be measured by the following method. First, the thickness (a) of the photocurable resin composition (A) layer and the thickness (b) of the base sheet (B) of the target photocurable sheet are measured. The thicknesses (a) and (b) can be measured by a method of observing a fracture surface of the photocurable sheet with an electron microscope or the like. Next, after weighing a sample of a photo-curable sheet of an appropriate size, this sheet sample is mixed with a predetermined amount of an appropriate extraction solvent and stirred, and after a tight stopper to prevent volatilization of each solvent, an appropriate time is obtained. put. The extraction solvent is preferably of a type different from the solvent that may remain in the photocurable sheet and capable of completely or partially dissolving and swelling the photocurable sheet. Next, the amount of solvent in the mixed solution is quantified by an analytical method such as gas chromatography, and the amount of solvent (Y) remaining in the photocurable sheet per unit mass is calculated. Finally, by substituting the respective numerical values of (a), (b), and (Y) thus obtained into the above formula (1), the solvent in the photocurable resin composition (A) per unit mass of the photocurable sheet. Calculate the quantity (X).

The amount (X) of solvent in the photocurable resin composition (A) per unit mass of the photocurable sheet is 10 or less, preferably 5 or less, more preferably 3 or less. When the amount of the solvent (X) exceeds 10, the surface of the photocurable resin composition (A) layer before light irradiation has tackiness, which causes problems in the printing process and storage stability in a roll state. And photo-curing resin composition (A) after the photo-curing, scratch resistance, chemical resistance, weather resistance and the like.

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

As the method for producing the photocurable sheet of the present invention, for example, the photocurable resin composition (A) is sufficiently stirred and dissolved in a solvent such as an organic solvent, and then gravure printing method, screen printing method, offset printing method. Coating on the base sheet (B) by a known printing method such as a coating method, a known coating method such as a knife coating method, a comma coating method, a reverse coating method, a dip coating method, and drying for removing the solvent. There is a method of forming a laminated sheet.

As the solvent for stirring and dissolving the photocurable resin composition (A), the components of the photocurable resin composition (A) are dissolved or uniformly dispersed, and the physical properties of the base sheet (B) are The solvent is not particularly limited as long as it is a volatile solvent that does not exert a serious adverse effect on (mechanical strength, transparency, etc.).
Examples of such a solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol, aromatic solvents such as xylene, toluene and benzene, and aliphatic hydrocarbon solvents such as hexane and pentane. Chloroform, halogenated hydrocarbon solvents such as carbon tetrachloride, phenol, phenol solvents such as cresol, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as acetone, diethyl ether, methoxytoluene, 1,2-dimethoxyethane,
1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane,
Ether solvent such as THF, formic acid, acetic acid, fatty acid solvent such as propionic acid, acid anhydride solvent such as acetic anhydride, ethyl acetate, butyl acetate, ester solvent such as butyl formate,
Nitrogen-containing solvent such as ethylamine, toluidine, dimethylformamide, dimethylacetamide, sulfur-containing solvent such as thiophene and dimethylsulfoxide, diacetone alcohol, 2-methoxyethanol (methylcellosolve),
2-ethoxyethanol (ethyl cellosolve), 2-butoxy ethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, a solvent having two or more functional groups such as morpholine, or various known solvents such as water A solvent can be used.

Further, when coating the above resin liquid on a base sheet made of polyolefin such as polyethylene or polypropylene, in order to improve the adhesion between the base sheet and the photocurable resin composition, (1) in advance , A primer such as a low molecular weight polyolefin is applied on the base material sheet, or (2) the surface of the base material sheet is activated in advance by corona discharge or the like. It is preferable that it is slightly before the coating, since it has a high adhesiveness immediately after being cured. Furthermore, in order to prevent the volume of the photocurable resin composition from shrinking during photocuring and to reduce the adhesion to the base sheet,
It is preferable to laminate a primer layer.

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

The printing layer is to decorate the surface of the molded product with patterns, characters and the like. The decoration is optional, for example,
Examples of the design include wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, and solid pattern. As the material of the printing layer,
Polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, It is preferable to use a colored ink containing a resin such as a chlorinated polyolefin resin as a binder and containing a pigment or dye of an appropriate color as a colorant.

As the pigment of the ink used in the printing layer, for example, the following can be used. Usually, as a pigment, an azo-based pigment such as polyazo as a yellow pigment, an organic pigment such as isoindolinone or an inorganic pigment such as yellow lead, an azo-based pigment such as polyazo as a red pigment, an organic pigment such as quinacridone or a rouge pattern. Inorganic pigments, organic pigments such as phthalocyanine blue as blue pigments, inorganic pigments such as cobalt blue, organic pigments such as aniline black as black pigments, and inorganic pigments such as titanium dioxide as white pigments can be used.

As the dye of the ink used in the printing layer, various known dyes can be used 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, 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, using a photocurable resin composition of the structure to crosslink the polymers, and the amount of solvent in the photocurable resin composition When (X) is made small, the surface has no tackiness, there are few troubles during printing, and the yield is good.

As a layer for decorating the surface of the molded article, a vapor deposition layer may be provided instead of the printing layer, or both the printing layer and the vapor deposition layer may be provided.

The vapor deposition layer is made of aluminum, nickel, gold,
Using at least one metal selected from the group consisting of platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, or an alloy or compound thereof, a vacuum deposition method, a sputtering method, an ion method. It can be formed by a method such as a plating method or a plating method.

The print layer and vapor deposition layer for these decorations are
In order to obtain a desired surface appearance of the molded product, its thickness may be appropriately selected according to the degree of extension during insert molding or in-mold molding.

Further, the photocurable sheet of the present invention may be a photocurable decorative sheet in which a printing layer and / or a vapor deposition layer, an adhesive layer and, if necessary, a primer sheet are formed on the base material sheet side. it can. In that case, the preferable thickness range of the photocurable decorative sheet is 30 to 750 μm.
If the sheet thickness is less than 30 μm, the sheet thickness on the curved surface may be significantly reduced when deep-drawing is performed, and as a result, sheet properties such as scratch resistance and chemical resistance may be reduced. Further, when the sheet thickness exceeds 750 μm, the shape followability to the mold may be deteriorated.

For the adhesive layer, any synthetic resin material can be selected and used as long as it has a property of enhancing the adhesion between the printed layer or the vapor-deposited layer and the molding resin, and the adhesiveness between the printed layer or the vapor-deposited layer and the primer sheet. be able to. For example, when the molding resin is a polyacrylic resin, a polyacrylic resin may be used. When the molding resin is a polyphenylene oxide / polystyrene resin, a polycarbonate resin, a styrene copolymer resin, or a polystyrene blend resin, a polyacrylic resin, a polystyrene resin, or a polyamide resin having an affinity for these resins. Etc. may be used. Further, when the molding resin is a polyolefin resin such as a polypropylene resin, a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, a coumarone indene resin, a heat using a blocked isocyanate is used. 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 contained for the purpose of reducing the tackiness of the adhesive layer and improving the heat resistance.

The above-mentioned primer sheet is formed as required, and is made of acrylic resin, polyester resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, chlorinated polyethylene. A known resin such as a system resin can be used. For the purpose of improving the adhesion to the molding resin, it is preferable to use a material compatible with the molding resin. In reality, the primer sheet is preferably made of the same or similar polymer material as the molding resin. In addition, the presence of the primer sheet provides the advantage that the surface defects of the injection-molded article are minimized from being propagated on the photocurable resin composition, and when the printing layer or the adhesive layer is present on the primer sheet. Has an advantage of preventing the thickness and pattern of each layer from being disturbed by the molten resin at the time of injection molding. In that case, the primer sheet preferably has a thickness sufficient to absorb surface defects of the molding resin while exhibiting a completely smooth upper surface of the photocurable resin composition, and the thickness thereof is in the range of 50 to 700 μm. It is preferable. The thickness of the primer sheet is 50
If it is less than μm, it may be difficult to sufficiently absorb surface defects on the surface of the molding resin. On the other hand, when the thickness of the primer sheet exceeds 700 μm, the conformability to the mold may be deteriorated.

In the photocurable sheet of the present invention, a cover film may be further provided on the photocurable resin composition (A) layer on the base material sheet (B). This cover film is effective in preventing dust on the surface of the photocurable sheet,
It is also effective for preventing scratches on the surface of the photocurable resin composition (A) layer before irradiation with active energy rays.

The cover film is in close contact with the photocurable resin composition (A) layer before insert molding or in-mold molding as described later, and is immediately peeled off during insert molding or in-mold molding. Therefore, it is preferable that the photocurable resin composition (A) layer has appropriate adhesion and good releasability. Any film can be selected and used as long as the film satisfies such conditions. Examples of such a film include a polyethylene film, a polypropylene film, a polyester film, and the like.

By the way, when a molded product such as an automobile body panel or spoiler has a large size and the molded product has a small thickness, the gas generated from the molded resin may remain in the molded resin, Air in the mold easily intervenes between the molding resin and the sheet, which may cause a problem that the adhesion of the sheet to the molding resin is deteriorated. 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 layer having gas permeability include a woven or non-woven fabric composed of spandex, acrylic fiber, polyethylene fiber, polyamide fiber and the like. Further, instead of the woven / nonwoven fabric, a foamed layer may be used. Examples of the method for forming the foam 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.

Next, an example of a method of manufacturing a molded article using the above-mentioned photocurable sheet or photocurable decorative sheet will be described.

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

The photocurable sheet or the photocurable decorative sheet is inserted and arranged so that the photocurable resin composition (A) side faces the inner wall surface of the mold (that is, the photocurable resin composition (A)). The other side of the layer is in contact with the molding resin). At this time, a necessary portion may be intermittently sent as a long sheet (while being unwound from a roll), or the sheet may be made into individual sheets and fed one by one. Especially when using a long sheet having a printing layer or a vapor deposition layer for decoration, use a feeder having a positioning mechanism so that the registration layer and the mold have the same register. Good to do. Also, when the sheet is intermittently fed, if the sheet position is detected by the sensor and then the sheet is fixed, the sheet can be fixed at the same position at all times, and the layer misalignment for decoration is displaced. This is convenient because it does not occur.

Then, if necessary, a photocurable sheet or a photocurable decorative sheet is preformed. For example, the sheet can be preformed by following the shape of the mold by softening the sheet above its softening point by a heating means such as a hot pack and performing vacuum suction through a suction hole provided in the mold. If the sheet is preheated to a temperature lower than the heat deformation temperature of the sheet before the sheet is inserted and arranged in the mold, the heating time after the sheet is inserted and arranged in the mold can be shortened. It becomes possible to improve productivity. Of course, it is also possible to simultaneously form the sheet and integrate it with the molding resin by injection pressure of the molding resin described later, without preforming the sheet. At this time, it is possible to preheat the sheet to soften it in advance.

By using a preforming die different from the injection molding die, a known forming method such as a vacuum forming method, a pressure forming method, a press forming method for pressing heated rubber, a press forming method, or the like is performed. After preforming the sheet into a desired shape in advance, the preformed sheet may be inserted and arranged in the molding die so that the photocurable resin composition side faces the inner wall surface of the die.

After that, the mold is closed, a molten molding resin is injected into the cavity, and the resin is solidified to obtain a molded product having a photocurable sheet or a photocurable decorative sheet on the surface. Form.

As the molding resin used in the present invention, any resin which can be injection-molded can be used regardless of its type. Examples of such a molding resin include polyethylene resin, polypropylene resin, polybutene resin,
Polymethylpentene resin, ethylene-propylene copolymer resin, ethylene-propylene-butene copolymer resin, olefin resin such as olefin thermoplastic elastomer, polystyrene resin, ABS (acrylonitrile / butadiene / styrene copolymer) ) Resin, AS
Examples include general-purpose thermoplastic or thermosetting resins such as (acrylonitrile / styrene copolymer) resins, acrylic resins, urethane resins, unsaturated polyester resins, and epoxy resins. In addition, general-purpose engineering resins such as polyphenylene oxide / polystyrene resin, polycarbonate resin, polyacetal resin, polycarbonate-modified polyphenylene ether resin, polyethylene terephthalate resin, polysulfone resin, polyphenylene sulfide resin, polyphenylene oxide resin, polyether A super engineering resin such as an imide resin, a polyimide resin, a liquid crystal polyester resin, or a polyallyl heat-resistant resin can also be used. Further, a composite resin or various modified resins to which a reinforcing material such as glass fiber or an inorganic filler (talc, calcium carbonate, silica, mica, etc.) or a modifier such as a rubber component is added can be used. It is preferable that the shrinkage rate of the molded resin after molding is approximated to the shrinkage rate of the sheet, because problems such as warpage and peeling of the sheet obtained by insert molding or in-mold molding can be eliminated.

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

The light to be applied is electron beam, ultraviolet ray, γ
A line etc. can be mentioned. The irradiation conditions are determined according to the photocuring characteristics of the photocurable resin composition (A) layer, but the irradiation amount is usually about 500 to 2,000 mJ / cm ² . Thereby, the photocurable resin composition is cured to obtain a molded product having a hard coating film formed on the surface thereof.

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

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

When the molded article decorated with the photocurable sheet of the present invention is mainly used outdoors, an ultraviolet absorber or a light stabilizer can be added to the sheet. As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, salicylate, etc., or a particle size of 0.2
Inorganic substances such as zinc oxide, cerium oxide, and titanium oxide in the form of fine particles of μm or less can be used. Further, as the light stabilizer, bis (2,2,6,6-tetramethyl-4
A hindered amine-based radical scavenger such as -piperidinyl) sebacate and a radical scavenger such as piperidine-based radical scavenger can be used.

The molded product thus obtained is given a color or a design at the same time as the molding, and further, the light resistance for a short time improves the abrasion resistance, the chemical resistance and the weather resistance. Further, compared with the conventional spray painting after molding, the process can be shortened, the yield can be improved, and the influence on the environment can be reduced.

The photocurable sheet of the present invention can also be used by laminating it on the surface of an adherend, either directly or through an adhesive layer, so as to be laminated on the surface of the adherend. The adherend may be a flat plate made of various materials, a plate material such as a curved plate, a sheet, a film, or various three-dimensional shaped articles (molded articles). For example, the photocurable sheet of the present invention can be used for a molded product having a curved surface such as an injection molded product. The adherend to which the photocurable sheet of the present invention is laminated can be further subjected to secondary processing such as vacuum forming.

Materials used as the adherend include wood veneer, wood plywood, particle board, wood boards such as medium density fiber board (MDF), wood board such as wood fiber board, metal such as iron and aluminum, Acrylic resin, polycarbonate resin, ethylene / vinyl acetate copolymer resin, ethylene vinyl acetate resin, polyester resin, polystyrene resin, polyolefin resin, ABS resin, phenol resin, polyvinyl chloride resin, cellulose Examples of the resin include resins such as resin and rubber.

Examples of the method of laminating the photocurable sheet of the present invention on each of these adherends include the following methods 1 to 4.

1. 1. A method of applying pressure to a plate-shaped or film-shaped substrate with a pressure roller and laminating it with or without an adhesive layer interposed therebetween. Japanese Patent Publication No. 56-45768, Japanese Patent Publication No. 60-58
As described in Japanese Patent Publication No. 014, etc., a photocurable sheet is placed on the surface of a molded product with or without an adhesive agent layer facing each other or placed, and vacuum suction is applied from the molded product side. 2. A so-called vacuum press laminating method in which a photocurable sheet is laminated on the surface of a molded article by a pressure difference. Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2666
As described in Japanese Patent Publication No. JP-A-2003-242, and the like, while supplying a photocurable sheet in the major axis direction of a columnar base material such as a cylinder or a polygonal column, with or without an adhesive agent layer in between, 3. A so-called lapping method in which a photocurable sheet is sequentially pressure-bonded and laminated on a plurality of side faces forming a columnar body by rollers having different directions. As described in JP-A-48-47972 and the like, first, a photocurable sheet is laminated on a plate-shaped substrate with or without an adhesive layer, and then the light of the plate-shaped substrate is laminated. A groove having a V-shaped or U-shaped cross section, which reaches the interface between the photocurable sheet and the plate-shaped substrate, is cut on the surface opposite to the curable sheet, and an adhesive is then placed in the groove. After coating, bend the groove to form a box or columnar body, so-called V
Cutting or U-cut processing method etc. are mentioned.

[0121]

EXAMPLES The present invention will be specifically described below based on examples. In the examples, “part” means “part by mass”.

Synthesis Example 1 (Synthesis of Thermoplastic Resin A Having Photopolymerizable Functional Group in Side Chain) 50 parts of methyl ethyl ketone was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer. The temperature was raised to 80 ° C. 67.8 parts of methyl methacrylate and 3 of glycidyl methacrylate under nitrogen atmosphere
A mixture of 2.2 parts and 0.5 part of azobisisobutyronitrile was added dropwise over 3 hours. Then, a mixture of 80 parts of methyl ethyl ketone and 0.2 parts of azobisisobutyronitrile was added and polymerized. 4 hours later, methyl ethyl ketone 50 parts, hydroquinone monomethyl ether 0.5
Part, 2.5 parts of triphenylphosphine and 16.2 parts of acrylic acid, and 30 at 80 ° C. while blowing air
Stir for hours. Then, after cooling, the reaction product was taken out from the flask to obtain a solution of the thermoplastic resin A having a photopolymerizable functional group in the side chain.

The polymerization rate of the monomer in the thermoplastic resin A having a photopolymerizable functional group in the side chain is 99.5% or more,
Polymer solid content is about 40% by mass, number average molecular weight is about 6
The glass transition temperature is about 77 ° C, and the double bond equivalent is 5 on average.
It was 18 g / mol.

Synthesis Example 2 (Synthesis of Thermoplastic Resin B Having Photopolymerizable Functional Group in Side Chain) 50 parts of methyl ethyl ketone was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer. The temperature was raised to 80 ° C. 41.3 parts methyl methacrylate and 5 glycidyl methacrylate under nitrogen atmosphere
A mixture of 8.7 parts, azobisisobutyronitrile 0.5 part and n-octyl mercaptan 2 parts was added dropwise over 3 hours. Then, a mixture of 80 parts of methyl ethyl ketone and 0.2 parts of azobisisobutyronitrile was added and polymerized. After 4 hours, 50 parts of methyl ethyl ketone, 0.5 parts of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 29.5 parts of acrylic acid were added, and the mixture was 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 B having a photopolymerizable functional group in its side chain.

The polymerization rate of the monomer in the thermoplastic resin B having a photopolymerizable functional group in the side chain is 99.5% or more,
Polymer solid content is about 42% by mass, number average molecular weight is about 6
10,000, glass transition temperature is about 54 ℃, double bond equivalent is 3 on average.
It was 16 g / mol.

Synthesis Example 3 (Synthesis of Thermoplastic Resin C Having a Photopolymerizable Functional Group in the Side Chain) In a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, under a nitrogen atmosphere. , 3,4-
Epoxy cyclohexyl methyl methacrylate 100
Parts, 60 parts of methyl ethyl ketone and 0.3 parts of azobisisobutyronitrile were added, the temperature of the water bath was raised to 75 ° C. with stirring, and polymerization was carried out at that temperature for 2 hours. Then
0.7 parts of azobisisobutyronitrile every 5 hours
After the addition in batches, the temperature inside the flask was raised to the boiling point of the solvent and polymerization was continued for another 2 hours at that temperature. Then, after the temperature inside the flask became 50 ° C. or lower, 90 parts of methyl ethyl ketone was added and the polymerization reaction product was taken out from the flask to obtain a solution of the thermoplastic resin C having a photopolymerizable functional group in the side chain.

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

Surface Treatment Example 1 of Colloidal Silica (Preparation of Surface Treated Colloidal Silica S1)

[0129]

[Table 2]

Note) Numerical values are molar parts in terms of solid content. 1) MEK-ST: Methyl ethyl ketone dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle size =
15 nm 2) KBM503: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248 The components shown in Table 2 above were put into a flask equipped with a stirrer, a condenser and a thermometer, and stirred. While raising the temperature of the hot water bath to 75 ° C. and reacting at that temperature for 2 hours, colloidal silica S1 dispersed in methyl ethyl ketone and having a surface treated with a silane compound was obtained.

Surface Treatment Example 2 of Colloidal Silica (Preparation of Surface Treated Colloidal Silica S2)

[0132]

[Table 3]

Note) Numerical values are molar parts in terms of solid content. 1) IPA-ST: isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle diameter = 1
5 nm 2) KBM503: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248 The components shown in the above Table 3 were put into a flask equipped with a stirrer, a condenser and a thermometer and stirred. While raising the temperature of the hot water bath to 75 ° C. and reacting at that temperature for 2 hours, colloidal silica dispersed in isopropanol and having a surface treated with a silane compound was obtained. continue,
Repeated addition of toluene after distilling off isopropanol to completely replace toluene with isopropanol gave colloidal silica S2 which was dispersed in toluene and whose surface was treated with a silane compound.

Examples 1 to 3 Thermoplastic resin A having a photopolymerizable functional group in the synthesized side chain
-C and the compounds of Table 4 were used to prepare photocurable resin solutions having the compositions of Table 4.

[0135]

[Table 4]

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

1) 1-Hydroxycyclohexyl phenyl ketone 2) Triphenylsulfonium hexafluoroantimonate Each of the resulting composition solutions was stirred with a propeller mixer to contain a crosslinked rubber component as a base sheet.
A transparent soft acrylic sheet (HBX-N47 manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 125 μm was applied to a coating width of 350 mm and dried under the conditions shown in Table 5 below to form a photocurable resin layer having a thickness of 8 μm. did.

[0138]

[Table 5]

Then, a slit is made to a width of 300 mm and 20
It was wound into a roll on an ABS core having a length of m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation upon heating at 100 ° C. was 26.
It was 0%.

Each of these photocurable sheets was replaced with 10
cm × 10 cm, cut and weighed, then N,
Immerse in 20 ml of N-dimethylformamide (containing methyl isobutyl ketone as internal standard) and leave overnight with stirring. The solution after standing overnight was analyzed by gas chromatography to measure the total amount of methyl ethyl ketone and toluene remaining in the photocurable resin composition. The results are shown in Table 6.

These photocurable sheets were placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, and then the sheet was preheated at an infrared heater temperature of 350 ° C. for 10 seconds, The sheet was made to follow the shape of the mold by vacuum suction while further heating. In addition,
The shape of this mold is a truncated pyramid, the size of the truncated surface is 100 mm x 100 mm, and the size of the bottom surface is 108 mm.
It was × 117 mm, the depth was 10 mm, and the radii of curvature at the ends of the truncated surface were 3, 5, 7, and 10 mm, respectively. At that time, the die followability was visually evaluated, and it was found that each end was following well.

Next, under the conditions of molding temperature of 280 to 300 ° C. and mold temperature of 40 to 60 ° C., in-mold molding was performed using a polycarbonate resin as a molding resin, and the photocurable sheet was adhered to the surface of the molded product. A molded product was obtained. At this time, stains on the molding die were visually evaluated.
The results are shown in Table 6.

Then, using an ultraviolet irradiation device, about 70
The photocurable resin composition was cured by irradiating it with ultraviolet rays of 0 mJ / cm ² , and the surface properties were evaluated. The results are shown in Table 6.

Further, after the roll was stored at room temperature for about 2 weeks, the tackiness of the surface was evaluated while unrolling. The results are shown in Table 6.

Sheet physical property evaluation method Acid resistance: A 47 mass% sulfuric acid aqueous solution was subjected to a spot test at 40 ° C. for 3 hours, and the appearance was visually evaluated.

◯: Good Δ: There is a thin mark ×: There is a marked mark Warm water resistance: The sheet state after being immersed in warm water of 80 ° C. for 24 hours was visually evaluated.

◯: Good Δ: Lightly whitened X: Significant whitening Transparency: According to ASTM D1003, total light transmittance and haze were measured using a haze meter.

Abrasion resistance: Taber abrasion test (500 on one side
g load, using CS-10F wear wheel, rotation speed 60 rp
m, the test was carried out 100 times, and the haze value was measured with a haze meter. And the numerical value represented by (haze value after test)-(haze value before test) was shown as abrasion resistance (%).

Weather resistance: Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the appearance was visually evaluated when exposed for 2000 hours in a cycle of 48 minutes of drying and 12 minutes of rain.

◯: Good ×: Whitening or cracks present Comparative Examples 1 to 3 Thermoplastic resin A having photopolymerizable functional group in synthesized side chain
-C and the compounds of Table 4 were used to prepare photocurable resin solutions having the compositions of Table 4. Example 1 except that drying after applying these photocurable resin solutions was performed under the conditions of Table 7.
A photocurable sheet and a molded product were obtained in the same manner as in the above-mentioned steps.
The evaluation results are shown in Table 6.

[0151]

[Table 6]

1) ○: No surface tackiness, Δ: Surface tackiness, ×: Large surface tackiness, unwinding 2) ○: No stain, Δ: Slight stain, ×: Large stain 3) Photocuring The total amount of methyl ethyl ketone and toluene in the photocurable resin composition per unit mass of the curable sheet 4) The abrasion resistance of the molded product obtained by in-molding only the transparent soft acrylic sheet having no photocurable resin layer is ,
It was 50%.

[0153]

[Table 7]

As shown in Table 6, in Comparative Examples in which the total amount of methyl ethyl ketone and toluene in the photocurable resin composition is large, the sheet surface has tackiness and causes poor storage stability in a roll state. Further, the mold stains during molding are remarkable. On the other hand, in the examples in which the total amount of methyl ethyl ketone and toluene is small, neither film has surface tackiness, is excellent in storage stability and moldability, has no mold stain, and has chemical resistance after curing,
Good transparency, abrasion resistance and weather resistance.

Examples 4 to 6 The composition solutions prepared in Examples 1 to 3 were each stirred by a propeller type mixer, and a transparent soft acrylic sheet (Mitsubishi Rayon (Mitsubishi Rayon ( Co., Ltd. HBX-N47) coating width 350m
m, and dried under the conditions shown in Table 5 above to a thickness of 20 μm.
m photocurable resin layer was formed. Then, as a cover film, a polyethylene film (manufactured by Tama Poly Co., GF
-14) was superposed so as to be in contact with the surface of the photocurable resin layer and passed between press rolls to obtain a laminated sheet in which the cover film and the sheet were integrated. Sequentially, slit the width to 300 mm and ABS to a length of 20 m.
It was wound into a core on a core.

These photocurable sheets were placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold after the polyethylene film of the cover film was peeled from the sheet, and then the infrared heater was used. Temperature 300 ℃
The sheet was preheated for 15 seconds. The sheet was made to follow the shape of the mold by vacuum suction while further heating.

Next, under the conditions of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C., in-mold molding is carried out using a polycarbonate resin as a molding resin, and the photocurable sheet is adhered to the surface of the molded product. I got the goods. At this time, both the mold followability and the mold releasability of the sheet were good.

Then, using an ultraviolet irradiation device, about 70
The photocurable resin composition was cured by irradiating with 0 mJ / cm ² of ultraviolet rays, and a molded product having high surface hardness and excellent gloss was obtained.

Examples 7 to 9 In-mold molded products were obtained in the same manner as in Examples 4 to 6 except that a PET film was used as the cover film, and then ultraviolet rays were irradiated to cure the photocurable resin composition. Let The obtained molded product had high surface hardness and excellent gloss.

Example 10 A polycarbonate sheet (Asahi Glass Co., Ltd.) was used as a base sheet.
Manufactured by Lexan 8010), an in-mold molded product was obtained in the same manner as in Example 1 and then irradiated with ultraviolet rays to cure the photocurable resin composition. The obtained molded product had high surface hardness and excellent gloss.

Examples 11 to 13 The composition solutions prepared in Examples 1 to 3 were each stirred with a propeller-type mixer, and a transparent soft acrylic sheet (Mitsubishi Rayon (Mitsubishi Rayon ( Co., Ltd. HBX-N47) coating width 350m
m, and dried under the conditions shown in Table 5 above to a thickness of 20 μm.
m photocurable resin layer was formed. Then, width 300mm
It was slit into 20 m and wound into a roll on an ABS core to a length of 20 m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation at 100 ° C. heating was 400%.

Then, a pattern was printed on the surface of the transparent soft acrylic sheet by the gravure printing method using inks composed of pigments of black, brown and yellow colors to obtain a photocurable decorative sheet. Since these sheets had no surface tackiness, printability was good. The thickness of the sheet was 223 μm.

These photocurable decorative sheets were placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, and then the sheet was preheated at an infrared heater temperature of 300 ° C. for 15 seconds. After that, the sheet was made to follow the shape of the mold by vacuum suction while further heating.

Next, under the conditions of a molding temperature of 220 to 250 ° C. and a mold temperature of 40 to 60 ° C., in-mold molding was carried out using an acrylonitrile / butadiene / styrene copolymer resin as a molding resin, and photocurable decoration was performed. A molded product in which the sheet was in close contact with the surface of the molded product was obtained. Thus, the mold followability and the mold releasability of the sheet were both good.

Then, using an ultraviolet irradiation device, about 70
The photocurable resin composition was cured by irradiating with 0 mJ / cm ² of ultraviolet rays to obtain a molded product having a high surface hardness, excellent gloss, a printed pattern and excellent design.

Example 14 The composition solution prepared in Example 1 was stirred with a propeller-type mixer to contain a crosslinked rubber component as a base sheet, and a thickness of 2 was obtained.
A transparent soft acrylic sheet (HBX-N47 manufactured by Mitsubishi Rayon Co., Ltd.) having a coating width of 350 mm was coated on the transparent soft acrylic sheet having a thickness of 20 μm, and a photocurable resin layer having a thickness of 20 μm was formed. . Subsequently, it was slit into a width of 300 mm and wound in a roll shape on an ABS core to a length of 20 m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation at 100 ° C. heating was 400%.

Next, a pattern was printed by a gravure printing method on the surface of the transparent soft acrylic sheet using inks composed of pigments of black, brown and yellow. Since this sheet had no surface tackiness, printability was good.

Further, an adhesive layer made of a chlorinated polypropylene resin (chlorination degree: 15%) was formed on the printing surface by a gravure printing method, and then a photocurable decorative sheet was obtained.
The thickness of the sheet was 255 μm.

This photocurable decorative sheet was placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold, and then the sheet was preheated at an infrared heater temperature of 300 ° C. for 15 seconds. The sheet was made to follow the shape of the mold by vacuum suction while further heating.

Next, polypropylene resin (containing 20% by mass of talc and 10% by mass of ethylene-propylene rubber) was used as a molding resin under the conditions of molding temperature of 200 to 240 ° C. and mold temperature of 30 to 60 ° C. In-mold molding was performed using the above to obtain a molded product in which the photocurable decorative sheet was in close contact with the surface of the molded product. Thus, the mold followability and the mold releasability of the sheet were both good.

Then, using an ultraviolet irradiation device, about 70
The photocurable resin composition is cured by irradiating with 0 mJ / cm ² of ultraviolet rays, and has high surface hardness and abrasion resistance, and excellent gloss.
A molded product having a printed pattern and excellent in design was obtained.

Example 15 The composition solution prepared in Example 1 was stirred with a propeller-type mixer to contain a crosslinked rubber component as a base sheet, and a thickness of 2 was obtained.
A transparent soft acrylic sheet (HBX-N47 manufactured by Mitsubishi Rayon Co., Ltd.) having a coating width of 350 mm was applied onto a 00 μm transparent soft acrylic sheet, and dried under the conditions shown in Table 5 above to form a photocurable resin layer having a thickness of 20 μm. Subsequently, it was slit into a width of 300 mm and wound in a roll shape on an ABS core to a length of 20 m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation at 100 ° C. heating was 400%.

Then, a pattern was printed on the surface of the transparent soft acrylic sheet by a gravure printing method using inks containing pigments of black, brown and yellow. Since this sheet had no surface tackiness, printability was good.

Separately from this, on one surface of a transparent polypropylene sheet (PA002 manufactured by Mitsubishi Kagaku MKV Co., Ltd.) having a thickness of 50 μm, which was subjected to corona discharge treatment on both surfaces,
An adhesive layer made of a chlorinated polypropylene resin (15% chlorination degree) was printed by a gravure printing method. Next, on the adhesive layer surface, set the respective sheets so that the printing surfaces of the photocurable sheet prepared above face each other, and pass them between the heating roll and the cooling roll for thermocompression bonding to integrate the respective sheets. A laminated sheet was obtained.

This laminated sheet was placed in the mold so that the photocurable resin composition faces the inner wall surface of the mold (however, the mold used in this example had a truncated pyramid shape, The size of the truncated surface is 50 mm x 50 mm, and the size of the bottom surface is 1.
(08 mm × 117 mm, depth is 3 mm), and then the sheet was preheated at an infrared heater temperature of 300 ° C. for 15 seconds, and then vacuum suction was performed while further heating to make the sheet follow the mold shape.

Next, polypropylene resin (containing 20% by mass of talc and 10% by mass of ethylene-propylene rubber) was used as a molding resin under the conditions of molding temperature of 200 to 240 ° C. and mold temperature of 30 to 60 ° C. In-mold molding was performed using the product to obtain a molded product in which the laminated sheet was in close contact with the surface of the molded product. Thus, the mold followability and the mold releasability of the sheet were both good.

Then, using an ultraviolet irradiation device, about 70
The photocurable resin composition is cured by irradiating with 0 mJ / cm ² of ultraviolet rays, and has high surface hardness and abrasion resistance, and excellent gloss.
A molded product having a printed pattern and excellent in design was obtained.

Example 16 The composition solution prepared in Example 1 was stirred with a propeller-type mixer to contain a crosslinked rubber component as a base sheet, and a thickness of 2 was obtained.
A transparent soft acrylic sheet (HBX-N47 manufactured by Mitsubishi Rayon Co., Ltd.) having a coating width of 350 mm was applied onto a 00 μm transparent soft acrylic sheet, and dried under the conditions shown in Table 5 above to form a photocurable resin layer having a thickness of 20 μm. Subsequently, it was slit into a width of 300 mm and wound in a roll shape on an ABS core to a length of 20 m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation at 100 ° C. heating was 400%.

Next, a pattern was printed on the surface of the transparent soft acrylic sheet by a gravure printing method using inks containing pigments of black, brown and yellow. Since this sheet had no surface tackiness, printability was good.

Separately from this, a chlorinated polypropylene resin (having a chlorination degree of 15%) was formed on one surface of a 100 μm thick transparent polypropylene sheet (PA002 manufactured by Mitsubishi Kagaku MKV Co., Ltd.) having corona discharge treatment on both sides. ) Was printed by a gravure printing method. Then, on the adhesive layer surface, set the respective sheets so that the printing surfaces of the photocurable sheet prepared above face each other,
It was passed between a heating roll and a cooling roll for thermocompression bonding to obtain a laminated sheet in which the respective sheets were integrated.

Next, an epoxy-isocyanate adhesive was applied and degreased to prepare a steel plate having a thickness of 1.0 mm. Then, the produced laminated sheet was superposed on a steel plate so that the photocurable resin composition layer of the laminated sheet appeared on the surface, and pressure-bonded. Then, using an ultraviolet irradiation device, the photocurable resin composition is cured by irradiating it with about 700 mJ / cm ² of ultraviolet light, and has high surface hardness and abrasion resistance, excellent gloss, and a printed pattern. A decorative steel sheet with excellent design was obtained.

Example 17 The composition solution prepared in Example 1 was stirred with a propeller-type mixer to contain a crosslinked rubber component as a base sheet, and a thickness of 2 was obtained.
A transparent soft acrylic sheet (HBX-N47 manufactured by Mitsubishi Rayon Co., Ltd.) having a coating width of 350 mm was applied onto a 00 μm transparent soft acrylic sheet, and dried under the conditions shown in Table 5 above to form a photocurable resin layer having a thickness of 20 μm. Subsequently, it was slit into a width of 300 mm and wound in a roll shape on an ABS core to a length of 20 m. When the breaking elongation of only the transparent soft acrylic sheet was measured by Tensilon, the breaking elongation at 100 ° C. heating was 400%.

Further, an adhesive layer made of a modified acrylic resin was formed on the surface of the transparent soft acrylic sheet opposite to the photocurable resin layer by a gravure printing method to obtain a photocurable sheet. The thickness of the sheet was 255 μm.

Separately from this, a printing layer using an ink composed of pigments of each color of black, brown and yellow is formed on the surface, and the thickness is 1.
Prepare a 0 mm ABS sheet, set each sheet so that the adhesive layer surface of the photocurable sheet prepared above faces this printed surface, and pass it between a heating roll and a cooling roll for thermocompression bonding. A laminated sheet in which the above sheets were integrated was obtained.

Then, the laminated sheet was vacuum-pressure formed into a desired shape so that the photocurable resin layer side of the obtained laminated sheet was the outermost layer. Finally, the photocurable resin composition is cured by irradiating it with an ultraviolet ray of about 700 mJ / cm ^{2 using} an ultraviolet ray irradiator, and has high surface hardness and abrasion resistance, excellent gloss, and a printed pattern. A molded product with excellent design was obtained.

[0186]

As described above, according to the present invention,
A surface-non-adhesive photo-curable printing sheet capable of printing a color or a design can be easily obtained, and by using the same at the time of injection molding, the color or the design or the like can be formed on the resin molded product. It has a design and can form a surface with good appearance, abrasion resistance, weather resistance and chemical resistance. Instrument panel, console box, meter cover, door lock bezel, steering wheel, power window switch base, center cluster ,
Automotive interior materials such as dashboards, weather strips, bumpers, bumper guards, side mudguards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, etc. , Windows, head lamp covers, tail lamp covers, automotive exterior materials such as windshield parts, front panels for AV equipment and home appliances, buttons, emblems, surface decorative materials, mobile phone housings, display windows, buttons, etc. , Further furniture exterior materials applications, wall surfaces, ceilings, floors and other architectural interior material applications, siding and other outer walls, fences, roofs, gates, gable boards and other architectural exterior material applications, window frames, doors, Applications for surface decorative materials such as handrails, sills, and Kamoi Play, lens, mirror,
Optical parts such as goggles, window glass, trains,
Suitable for use in interior / exterior materials of various vehicles other than automobiles such as airplanes and ships, various packaging containers and materials such as bottles, cosmetic containers, accessory cases, miscellaneous goods such as gifts and accessories, etc. it can. Further, on the transparent resin, it is possible to form a surface having good abrasion resistance, weather resistance and chemical resistance while making use of its transparency, and a window or headlamp cover of an automobile, a railroad vehicle, an airplane or the like, It can be suitably used for windshield parts and the like. In addition, the number of steps can be omitted as compared with the case of coating the surface of the molded product, the productivity is good, and the influence on the environment is small.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kenji Suemura             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Central Technology Research Institute F-term (reference) 4F100 AA00B AA00H AA20B AA20H                       AK01B AL07B AR00E AT00A                       BA02 BA05 BA07 BA10B                       BA10E CA23B CA30B DE01B                       DE01H EH36 EH66D EJ52                       GB07 GB31 GB32 GB48 GB90                       HB31C JA20B JB01 JB14B                       JB14K JB16B JK09 JL09                       JL10 JL11E YY00B                 4F206 AA28 AD05 AD09 AF10 AG03                       JA07 JB13 JB19 JF05 JL02                       JW41                 4J027 AA02 BA01 CB10 CD01

Claims (17)

[Claims] 1. A photocurable sheet comprising a layer of the photocurable resin composition (A) and a base sheet (B), wherein the photocurable resin composition (A) represented by the following formula (1): A photocurable sheet having a solvent amount (X) of 10 or less. X = Y / (a / (a + b)) (1) Here, X is the amount of the solvent in the photocurable resin composition (A) per unit mass of the photocurable sheet, and a is the photocurable resin composition. The film thickness (μ) of the material (A) layer, b is the thickness (μ) of the base material sheet (B), and Y is the amount of solvent per unit mass of the photocurable sheet. 2. The photocurable resin composition (A) contains a thermoplastic resin (a-1) having a photopolymerizable functional group in a side chain and a photopolymerization initiator (a-2), and (a- The photocurable sheet according to claim 1, which is substantially free of a crosslinkable compound other than 1). 3. The photocurable sheet according to claim 2, wherein the side-chain photopolymerizable functional group of the thermoplastic resin (a-1) is a radically polymerizable unsaturated group. 4. The photocurable sheet according to claim 2, wherein the side-chain photopolymerizable functional group of the thermoplastic resin (a-1) is an alicyclic epoxy group. 5. The photocurable sheet according to claim 1, wherein the photocurable resin composition (A) further contains inorganic fine particles (a-3). 6. The photocurable sheet according to claim 5, wherein the inorganic fine particles (a-3) are colloidal silica. 7. The cover film is temporarily adhered to the photocurable resin composition (A) layer side.
7. The photocurable sheet according to any one of to 6. 8. A printed layer and / or a print layer formed on the base sheet side of the photocurable sheet according to claim 1.
Alternatively, a photocurable decorative sheet including a vapor deposition layer. 9. A print layer and / or a print layer formed on the base sheet side of the photocurable sheet according to claim 1.
Alternatively, a photocurable decorative sheet including a vapor deposition layer and an adhesive layer. 10. A photocurable decoration comprising a printing layer and / or a vapor deposition layer formed on the substrate sheet side of the photocurable sheet according to claim 1, and an adhesive layer and a primer sheet. Sheet. 11. A photo-curable sheet or a photo-curable decorative sheet according to claim 1, which is inserted and arranged so that the photo-curable resin composition (A) side faces the inner wall surface of the mold. A step of closing the mold, injecting a molten resin into the mold, and solidifying the resin to form a resin-molded article having a photocurable sheet or a photocurable decorative sheet on the surface thereof, And a method for producing a molded article, which comprises a step of photo-curing the photocurable resin composition on the surface of the molded article by irradiating with light. 12. The method for producing a molded article according to claim 11, further comprising a step of peeling and removing the cover film in advance. 13. A photo-curable sheet or a photo-curable decorative sheet according to claim 1, wherein the photo-curable resin composition (A) side is inserted and arranged so as to face the inner wall surface of the mold. Step of preforming a photocurable sheet or a photocurable decorative sheet to make the sheet conform to the mold shape, closing the mold, injecting molten resin into the mold, and solidifying the resin Molding including a step of forming a resin molded article having a photocurable sheet or a photocurable decorative sheet on the surface thereof, and a step of photocuring the photocurable resin composition on the surface of the molded article by irradiation with light. Method of manufacturing goods. 14. The method for producing a molded article according to claim 13, further comprising a step of peeling and removing the cover film in advance. 15. A mold for preforming of the photocurable sheet or the photocurable decorative sheet according to claim 1, wherein the photocurable resin composition side faces the inner wall surface of the mold. The photocurable sheet or the photocurable decorative sheet, and the step of preforming the photocurable sheet or the photocurable decorative sheet so that the sheet follows the mold shape, and photocuring the preformed photocurable sheet or the photocurable decorative sheet. Step of inserting and placing in a molding die so that the resin composition side faces the inner wall surface of the die,
Closing the molding die, injecting a molten resin into the die, and solidifying the resin to form a photocurable sheet or a photocurable decorative sheet to form a resin molded article having a surface disposed thereon; and A method for producing a molded article, which comprises a step of photo-curing the photocurable resin composition on the surface of the molded article by irradiating with light. 16. The method for producing a molded article according to claim 15, further comprising a step of peeling and removing the cover film in advance. 17. A molded product obtained by the manufacturing method according to claim 11.