JP2002275205A - Method for producing resin molded article having periodical wrinkle pattern on surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin molded article having a periodical wrinkle pattern on the surface, such as a sufficiently cured coating film having a relatively thick coating film thickness and a fine wrinkle pattern on the surface, a molded article which exhibits transparency but whose surface is mat (non-reflective), or a uniformly cloudy frost glass-like molded article. SOLUTION: This method for producing a resin molded article having a periodical wrinkle pattern on the surface comprises irradiating a photocurable resin composition comprising (A) a photocross-linking compound, (B) a chain polymer and (C) a photopolymerization initiator exhibiting a light-absorbing property at two wavelengths W1 and W2 (250 nm<W1<W2<410 nm) and having molar absorbance coefficients 3,000 (L.mol<-1> .cm<-1> ) and 150 to 5 (L.mol<-1> .cm<-1> ) at W1 and W2, respectively, with active light having an optical power of >=10 mM/cm<2> at wavelengths W1 and W2, respectively, at a temperature giving a composition viscosity of <=100,000 Pa.s to cure the composition at one step.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating film having a wrinkle pattern on the surface. The present invention relates to a surface treatment for building materials, interiors of vehicles and the like, glass decorations, housings of electric and electronic equipment, and the like. In coating and painting, by forming fine wrinkles on the surface of the coating film or molded product, it is used for the purpose of improving the light diffusion effect, designability and aesthetic appearance, or forming a relatively large wrinkle pattern and homogeneously By making it cloudy, it is used as a receiving layer for recording paper, a waveguide plate, or the like.

[0002]

2. Description of the Related Art Conventionally, in order to improve the design and aesthetics of molded products, attempts to make the surface of an object to be coated a matte state by a light diffusing effect with various surface treatment agents have conventionally been conducted using paints. Or matt pigments in ink or ink,
It has been used for a long time by methods such as surface blasting.

However, the method of incorporating a matting pigment into a coating resin, ink or the like has a disadvantage that the light transmittance of a cured coating film is reduced and the coating film is necessarily opaque. In addition, the blasting process is complicated and has a problem in productivity. In addition, when using an ultraviolet curable resin excellent in curability and productivity, perform ultraviolet irradiation in a nitrogen atmosphere,
A method of matting by a method of generating wrinkles is known. However, ultraviolet irradiation in a nitrogen atmosphere requires a special device in addition to the cost of nitrogen, and thus has a problem that the cost increases.

[0004] Japanese Patent Application Laid-Open No. Hei 6-313495 discloses 30
A method of generating wrinkles by ultraviolet light of 0 nm or less is disclosed. However, simply irradiating with ultraviolet light of a short wavelength has a problem that the system in which wrinkles are formed is limited, the size and structure of wrinkles are difficult to control, and only a thin film-like molded product is obtained. Japanese Patent Application Laid-Open No. 9-53024 discloses a method using an acrylate compound having a hydroxyl group. However, this method is a method for a specific compound, and has a problem that it cannot be applied to a wide variety of actinic ray-crosslinkable polymerizable compounds.

Japanese Patent Application Laid-Open No. 55-5997 discloses that
A method is disclosed in which a matte surface is obtained by curing the inside of a coating film with low-intensity ultraviolet rays in an oxygen atmosphere and then curing the coating film surface with high-intensity ultraviolet rays. But,
This method has a problem that the size and depth of the wrinkles on the surface of the formed coating film cannot be controlled, and a problem that the cost is increased due to irradiation of ultraviolet rays in two stages.

[0006]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is that it can be applied to various photocrosslinkable polymerizable compounds.
In addition, even if the coating film has a relatively thick film thickness, a sufficiently cured coating film having a fine wrinkle pattern on the surface can be obtained, and a molded product having a matte surface (non-reflective) while exhibiting transparency. Another object of the present invention is to provide a method for producing a resin molded product having a periodically wrinkled pattern on its surface, which gives a frosted glass-like molded product that is uniformly clouded.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a photocurable composition comprising a photocrosslinkable polymerizable compound, a chain polymer, and a photopolymerization initiator having a specific light absorbing property. By irradiating the active resin composition with actinic rays, it was found that a wrinkle pattern having periodicity was formed on the surface of the coating film, and the present invention was completed.

That is, the present invention provides (A) a photocrosslinkable polymerizable compound, (B) a chain polymer, and (C) two wavelengths W1 and W2.
2 (250 nm <W1 <W2 <410 nm), exhibiting a light absorption property, a molar extinction coefficient of 3000 (L · mol ⁻¹ · cm ⁻¹ ) or more for W1, and 150 to 5 (L · m) for W2.
ol ^-1 · cm ^-1 ) of a photocurable resin composition containing a photopolymerization initiator having a molar extinction coefficient of 10
At a temperature of 0000 Pa · s or less, the composition is irradiated with an actinic ray having a light intensity of 10 mW / cm ² or more at wavelengths W1 and W2, and the composition is cured in one step. This is a method for producing a resin molded product having the same.

In the production method of the present invention, the mixing weight ratio of (A) the photocrosslinkable polymerizable compound and (B) the chain polymer is preferably (A) :( B) = (90:10) to (90:10). 20:80)
And (C) the photopolymerization initiator is preferably used in an amount of 15 parts by weight or less based on 100 parts by weight of the photocrosslinkable polymerizable compound.

Further, in the manufacturing method of the present invention, two wavelengths W
1 and W2 are 250 nm <W1 <310 nm, 350 n
The photocurable resin composition containing a photopolymerization initiator satisfying m <W2 <410 nm has a thickness of 100 ± 20 μm and has a parallel light transmittance between 260 and 380 nm.
The parallel light transmittance at the wavelength W1 is 20% or less, the parallel light transmittance at the wavelength W2 is 70% or more, and the wavelength W It is preferable to use a photopolymerization initiator having a molar extinction coefficient of 1000 (L · mol ⁻¹ · cm ⁻¹ ) or less in a wavelength region of (nm) to 500 nm.

Further, in the production method of the present invention, the (B) chain polymer used is preferably one kind selected from the group consisting of a polysulfone polymer, an aromatic polyester polymer, a styrene copolymer and a phenoxy resin. It is characterized by the above.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cause of the formation of a periodic wrinkle pattern on the surface of a molded article of the photocurable resin composition of the present invention is unknown, but it is probably that the photocurable resin composition is cured by ultraviolet light having a short wavelength of W1. A thin film is formed on the surface of the molded article of the conductive resin composition,
Next, it is considered that volume shrinkage occurs when the inside of the molded article of the photocurable resin composition is cured by the ultraviolet light having a long wavelength of W2, and a periodic wrinkle pattern is formed due to elastic instability during the volume shrinkage. .

Whether a periodic wrinkle pattern is formed, or the size and depth of the wrinkle pattern depends on the thickness and elastic modulus of the film on the surface, the viscosity and volume shrinkage of the photocurable resin composition, and the like. It is considered to depend on the contraction speed and the like. Here, the periodic wrinkle pattern of the present invention refers to wrinkles formed on the surface, that is, irregularities having periodicity, and the distance between a concave portion and an adjacent concave portion (hereinafter, this distance is simply referred to as “distance”. (Referred to as “wrinkle distance”) is periodic.

When the distance between wrinkles according to the present invention is measured one by one,
Although there is a certain degree of variation, the variation in the distance between ten consecutive wrinkles is 30% or less of the average value of the distance between the ten wrinkles. These are preferably at most 20%, particularly preferably at most 10%. By reducing the variation in the distance between wrinkles, a matte (non-reflective) molded article having good transparency can be obtained, and a matte state excellent in moist texture can be obtained.

The periodicity of the wrinkle pattern according to the present invention includes a periodicity in only one direction of the surface, and when the wrinkle pattern has a structure in which long and thin wrinkles are close to each other, the periodicity only occurs during a distance between adjacent wrinkles. Includes those that show sex. The average value of the distance between wrinkles is referred to as a correlation length, and the correlation length of the wrinkle pattern of the molded product according to the production method of the present invention is 0.2 to 50 μm, preferably 0.4 to 2 μm.
It is 0 μm. If it exceeds 50 μm, the periodicity deteriorates, and if it is less than 0.2 μm, the depth of the wrinkles becomes too small, and optical characteristics such as matting do not occur.

The resin molded product obtained by the production method of the present invention can be obtained from an optically highly transparent one to a cloudy one. The transparency of the resin molded product is mainly correlated with the depth of the wrinkles. When the depth of the wrinkles is small, the transparency is improved while matting. In the case of a resin molded product having transparency, it is preferably used as a matte film or a coating film.
On the other hand, when the depth of the wrinkles on the surface is increased, the transparency of the resin molded product is lost, and the resin molded product is uniformly opaque and becomes a ground glass-like molded product.

In order to obtain a molded article having high transparency, the depth of the wrinkles is preferably 0.05 to 20 μm, particularly 0.1 to 10 μm.
μm is preferred. When the thickness is less than 0.05 μm, the effect of the matte surface is hardly exhibited. The depth of the wrinkles on the surface can be determined by observing the cross section of the coating film with an electron microscope or a laser microscope, and when the depth of the wrinkles is shallow, a contact surface roughness meter or a tunnel microscope.

The resin molded product having a periodic wrinkle pattern on the surface of the present invention is suitable for a film or a coating film. According to the production method of the present invention, although the thickness of the film or coating film is relatively large, a wrinkled structure on the surface is formed even if the thickness is large, but the thickness is preferably 1 mm or less, more preferably from the viewpoint of taking advantage of the characteristics of the ultraviolet curable resin. Preferably 0.5 mm or less, particularly preferably 0.5 mm.
3 mm or less. Further, the lower limit of the film thickness is preferably 1 μm, particularly preferably 2 μm or more. 1μ thickness
If it is less than m, it is difficult to form a wrinkle pattern, which is not preferable.

The photocrosslinkable polymerizable compound (A) used in the present invention is a compound which is polymerized by actinic rays such as ultraviolet rays or visible rays to form a crosslinked polymer, and has radical polymerizability, anion polymerizability, cationic polymerizability and the like. It may be arbitrary. As the photocrosslinkable polymerizable compound, a compound which is crosslinked and polymerized by actinic light in the presence of a photopolymerization initiator is usually used, but a compound which is crosslinked and polymerized in the absence of a photopolymerization initiator can also be used.

As the photocrosslinkable polymerizable compound, those having two or more polymerizable carbon-carbon double bonds in the molecule are preferable, and among them, highly reactive (meth) acrylic compounds, vinyl ethers, A maleimide-based compound is preferably used as a self-photocrosslinkable polymerizable compound that cures even in the absence of a polymerization initiator.

The photocrosslinkable polymerizable compound can be used alone or in combination of two or more. Also,
A resin molded product of the present invention cannot be formed by itself, and may be formed only when mixed with other components, for example, a solid compound. Further, in order to control hardness, reactivity and the like, a monofunctional photopolymerizable compound which does not give a crosslinked polymer by itself can be mixed and used.

The (meth) acrylic monomer which can be preferably used as the photocrosslinkable polymerizable compound includes, for example, diethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,8
-Octanediol di (meth) acrylate, 2,2 '
-Bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, neopentylglycol hydroxydipivalate di (meth) acrylate, di Cyclopentanyl diacrylate,

Bifunctional monomers such as bis (acryloxyethyl) hydroxyethyl isocyanurate and N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth)
Trifunctional monomers such as acrylate, tris (acroxyethyl) isocyanurate, and caprolactone-modified tris (acroxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meta) And 6) a hexafunctional monomer such as acrylate.

As the photocrosslinkable polymerizable compound, a crosslinkable polymerizable oligomer (also referred to as a prepolymer) can be used.
50,000. Examples of such cross-linkable polymerizable oligomers include (meth) acrylates of epoxy resins, (meth) acrylates of polyether resins, (meth) acrylates of polybutadiene resins, Examples thereof include polyurethane resins having a (meth) acryloyl group.

Examples of the maleimide-based photocrosslinkable polymerizable compound, which is a self-photocrosslinkable polymerizable compound, include 4,4′-methylenebis (N-phenylmaleimide) and 2,3-bis (2,4 , 5-trimethyl-3-thienyl) maleimide, 1,2-bismaleimidoethane,
1,6-bismaleimide hexane, triethylene glycol bismaleimide, N, N'-m-phenylenedimaleimide, m-tolylenedimaleimide, N, N'-1,4
Phenylenedimaleimide, N, N′-diphenylmethane dimaleimide, N, N′-diphenylether dimaleimide,

N, N'-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride,
Bifunctional maleimides such as 4,4'-isopropylidenediphenyl dicyanate.N, N '-(methylenedi-p-phenylene) dimaleimide; polymerizable functionalities other than maleimide groups such as N- (9-acridinyl) maleimide and maleimide groups And a maleimide having a group.

Examples of the maleimide-based crosslinked polymerizable oligomer include polytetramethylene glycol maleimide alkylate such as polytetramethylene glycol maleimide capryate and polytetramethylene glycol maleimide acetate.

The photocrosslinkable polymerizable compound preferably has 2 to 6 (meth) acryloyl groups or maleimide groups in the molecule, and has a molecular weight (average molecular weight in the case of those having a molecular weight distribution) of 100 to 100. Those which are 1000 compounds are preferred. When the molecular weight exceeds this range, the strength of the obtained resin molded article tends to decrease.

The monofunctional photopolymerizable compound can be used as a viscosity modifier for the photocurable resin composition. Monofunctional (meth) acrylic monomers that can be used as a monofunctional photopolymerizable compound include, for example, methyl and methacrylate and alkyl (meth) which are known and commonly used.
Acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate,
Alkylphenoxy polyethylene glycol (meth) acrylate,

Nonylphenoxy polypropylene glycol (meth) acrylate, hydroxyalkyl (meth)
Acrylate, glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-
Acryloyloxyethyl-2-hydroxypropyl acrylate, ethylene oxide-modified phthalic acid acrylate,

Ω-alkoxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloysoxypropyl hexahexahydrohydrogen phthalate, fluorine-substituted alkyl (meth) Acrylate, chlorine-substituted alkyl (meth) acrylate, (meth) acrylate having a silano group, and the like can be given.

Examples of the monofunctional maleimide monomer which can be used as the monofunctional photopolymerizable compound include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide. N-alicyclic maleimides such as N-cyclohexylmaleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide;
N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide,

2,3-dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2
N- such as -ethyl-6-methylphenyl) maleimide
(Substituted or unsubstituted phenyl) maleimide; maleimide having a halogen such as N-benzyl-2,3-dichloromaleimide and N- (4′-fluorophenyl) -2,3-dichloromaleimide; and hydroxyl group such as hydroxyphenylmaleimide. Maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide;

Maleimide having an alkoxy group such as N-methoxyphenylmaleimide; maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide; polycyclic aromatic maleimide such as N- (1-pyrenyl) maleimide A maleimide having a heterocyclic ring such as N- (dimethylamino-4-methyl-3-coumarinyl) maleimide and N- (4-anilino-1-naphthyl) maleimide;

The chain polymer (B) used in the present invention is uniformly mixed with the photocrosslinkable polymerizable compound (A) used in a temperature range for irradiating an actinic ray described below, and
It is inert to the actinic rays used. The term "inactive with respect to actinic rays" means that substantially no crosslinking or decomposition reaction occurs. In the present invention, the chain polymer refers to a polymer that is not a crosslinked polymer, and includes a linear polymer and a branched polymer. The chain polymer used in the present invention may be amorphous or crystalline. Of course, the chain polymers can be used alone or as a mixture of two or more.

Examples of the chain polymer (B) that can be used in the resin composite of the present invention include polystyrene, poly-α-methylstyrene, styrene / maleic acid copolymer, styrene / acrylonitrile copolymer, styrene / Styrene polymers such as methyl methacrylate copolymer; polysulfone polymers such as porsulfone and polyether sulfone; poly (meth) acrylate polymers such as polymethyl methacrylate, polybutyl methacrylate, and polymethyl acrylate; polyacrylonitrile-based polymers Coalescence; polymaleimide-based polymer;

Polycarbonate polymers such as bisphenol A type polycarbonate and bisphenol Z type polycarbonate; cellulose derivatives such as nitrocellulose, cellulose acetate and ethyl cellulose; vinyl acetate polymers such as polyvinyl acetate and ethylene-vinyl acetate copolymer; Thermoplastic polyurethane polymers; polyvinyl chloride, polyvinylidene chloride, chlorine-containing polymers such as chlorinated polyethylene and chlorinated polypropylene; polyamide polymers; polylactic acid polymers; polyimide polymers; polyphenylene oxide;

Polyether and polythioether polymers such as polyphenylene sulfide / polysulfone copolymer; aromatic polyester polymers obtained from terephthalic acid and isophthalic acid; polyester polymers such as polycaprolactone; phenoxy resins; Polyethylene glycol polymer, polyvinyl pyrrolidone polymer; vinyl acetal polymer such as polyvinyl formal and polyvinyl butyral; diene rubber such as butadiene rubber, acrylonitrilo-butadiene rubber, styrene-butadiene rubber; chloroprene rubber, isoprene rubber Prene rubber; uncrosslinked rubber such as acrylic rubber;

The chain polymer (B) used in the present invention comprises:
Among them, styrene polymers such as styrene / maleic acid copolymer, styrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, polysulfone polymers such as porsulfone, polycarbonate polymers, aromatic polyesters Polymers, phenoxy resins and the like are particularly preferred.

The mixing weight ratio of (A) the photocrosslinkable polymerizable compound and (B) the chain polymer is (photocrosslinkable polymerizable compound: chain polymer) = (90:10) to (20:80). Preferably, (80:20) to (25:75) are particularly preferred. When the ratio of the chain polymer is out of this range, it is difficult to form a periodic wrinkle pattern, which is not preferable.

In the present invention, a periodic wrinkle pattern can be formed by using a chain polymer and controlling the amount of the polymer used, and the depth and size of the wrinkle can be easily controlled. It becomes possible. This is shown in detail in the embodiments. It is presumed that the photocrosslinkable polymerizable compound undergoes a large volume shrinkage during polymerization, but the chain polymer has a small volume shrinkage and includes those that do and do not undergo volume shrinkage, so that a wrinkled structure is likely to occur on the surface.

In the present production method, when the photocurable resin composition is cured by irradiation with light, phase separation between the crosslinked polymer of the photocrosslinkable polymerizable compound and the chain polymer often occurs. Good surface wrinkles are formed when they occur. Also, since there are many controllable factors for causing phase separation, it is easy to control the structure of wrinkles. That is, as the amount of the chain polymer (B) increases, the size of the wrinkles tends to decrease. In addition, the smaller the amount of the chain polymer used, the smaller the wrinkles tend to be.

The actinic ray used in the present invention is 2
A light intensity of at least 10 mW / cm ² in at least two wavelength regions (W1 and W2) between 50 nm and 410 nm;
It is preferably at least 20 mW / cm ² , particularly preferably 30 mW / cm ^2.
A light source having a mW / cm ² or more is used, and ultraviolet rays, visible rays, and rays such as infrared rays may be mentioned. From the viewpoint of handleability and equipment price, ultraviolet rays or visible rays are preferable.
Particularly, ultraviolet rays are preferable.

As the light source, a discharge lamp or an electrodeless lamp which generates a spectrum in a wavelength region of 200 to 600 nm can be used. As the lamp, a mercury lamp is preferably used, and a high-pressure mercury lamp, a low-pressure mercury lamp,
Metal halide lamps and super metal halide lamps are exemplified. As the electrodeless lamp, a xenon lamp or a xenon-mercury lamp is preferably used.

These ultraviolet sources have a high intensity emission line at a specific wavelength, and it is particularly preferable to use this emission line. Since the ultraviolet spectrum is substantially determined by the type of the ultraviolet light source, the intensity of the ultraviolet light near 365 nm can be estimated by measuring the intensity of the bright line around 365 nm.

In the manufacturing method of the present invention, 250 nm <W1
<W2 <410 nm wavelength W1 (nm) and W
At 2 (nm), the molar extinction coefficient at W1 on the shorter wavelength side is 3000 (L · mol ⁻¹ · cm ⁻¹ ) or more, preferably 40
00 (L · mol ⁻¹ · cm ⁻¹ ) or more, and the molar extinction coefficient is 150 to 5 (L · mol ⁻¹ ·
cm ⁻¹ ), preferably 100 to 8 (L · mol ⁻¹ · cm)
^-1 ) is used.

The molar extinction coefficient at the short wavelength side W1 is 3000
(L · mol ⁻¹ · cm ⁻¹ ), and when the molar extinction coefficient is out of the range of 150 to 5 (L · mol ⁻¹ · cm ⁻¹ ) on the long wavelength side W2, a wrinkle pattern is not formed well, which is preferable. Absent. The molar extinction coefficient at W1 on the short wavelength side is 3000 (L ·
mol ⁻¹ · cm ⁻¹ ), a good film is not formed, and the molar extinction coefficient in the long wavelength region W2 is 1
When the curing rate is outside the range of 50 to 5 (L · mol ⁻¹ · cm ⁻¹ ), the curing speed inside the molded body is reduced, so that it is estimated that the volume shrinkage does not occur favorably and the wrinkle pattern is not formed.

When a mercury lamp is used as the ultraviolet light source, any one of the spectra around 254 nm, 302 nm, 313 nm, 365 nm, and 405 nm, particularly preferably around 254 nm, 302 nm, 313 nm, 365 nm Any of the spectra are used. Therefore, it is preferable to select a photopolymerization initiator so that these wavelengths are W1 and W2.

The molar extinction coefficient is 1000 (L · mol ⁻¹ · cm ⁻¹ ), particularly 800 (L · mol ⁻¹ · cm ⁻¹ ) in the wavelength range of W to 500 nm where the light transmittance of the photocurable resin composition described below is 50%. L · mol ⁻¹ · cm ⁻¹ ) or less is preferably used. Exceeding this range is not preferred because the film formed on the surface of the molded product may be too thick to form a wrinkle pattern.

The above-mentioned photopolymerization initiator used in the production method of the present invention may be, for example, a radical polymerization initiator, an anionic polymerization initiator or a cationic polymerization initiator. Examples of such a photopolymerization initiator include benzophenone (15000 at 254 nm (L · mol ⁻¹ · cm ⁻¹ ),
140 at 313 nm (L · mol ⁻¹ · cm ⁻¹ ), 365
Benzophenones such as 90 (L · mol ⁻¹ · cm ⁻¹ ) at ¹ nm and 1-hydroxycyclohexyl phenyl ketone (6800 (L · mol ⁻¹ · c at 254 nm)
m ⁻¹ ), 90 at 313 nm (L · mol ⁻¹ · cm ⁻¹ ),
20 at 365 nm (L · mol ⁻¹ · cm ⁻¹ )),

2-hydroxy-2-methyl-1-phenylpropan-1-one (6670 at 254 nm (L · m
ol ^-1 · cm ^-1 ) at 313 nm 90 (L · mol ^-1 ·
cm ⁻¹ ), 12 at 365 nm (L · mol ⁻¹ · c)
such acetophenones of m ^-1)); benzyl dimethyl ketal ^{(254nm 12100 (L · mol -1} · cm
^-1 ) and benzoins such as 95 (L · mol ⁻¹ · cm ⁻¹ ) at 365 nm. These can be used alone or as a mixture.

The photopolymerization initiator can be used in a state of being dissolved or dispersed in the photocurable resin composition, but is preferably one that is soluble in the photocurable resin composition. The amount of the photopolymerization initiator to be used depends on the type of the photopolymerization initiator to be used and the like.
Usually, 0.1 part by weight based on 100 parts by weight of the photocrosslinkable polymerizable compound.
The range is preferably from 1 to 15 parts by weight, particularly preferably from 0.2 to 10 parts by weight.

The amount of the photopolymerization initiator is 10 or more.
Exceeding 15 parts by weight with respect to 0 parts by weight is not preferred because the film formed on the surface of the molded product becomes too thick to form a wrinkle pattern. If the amount of the photopolymerization initiator is less than 0.1 part by weight, the coating film is not sufficiently cured, which is not preferable. However, this is not always the case, for example, when a photocrosslinkable polymerizable compound also functions as a photopolymerization initiator, such as a maleimide compound, or when the photocrosslinkable polymerizable compound is a photopolymerization initiator copolymerized with an actinic ray crosslinkable polymerizable compound.

In the present invention, it may be possible to control the size of wrinkles depending on the amount of the photopolymerization initiator used. In this case, the larger the amount of the photopolymerization initiator, the smaller the wrinkles tend to be. Further, in order to increase the degree of curing of the coating film surface, it is preferable to perform the irradiation with the actinic ray in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

The photocurable resin composition used in the production method of the present invention has two wavelengths W1 and W2 (250 nm <W1 <3).
10 nm, exhibiting light absorption at 350 nm <W2 <410 nm, and 3,000 (L · mol ⁻¹ · c) at W1
m ^-1 ) or more, and 150 to 5 (L
· Includes a photopolymerization initiator having a molar extinction coefficient of mol ^-1 · cm ^-1), thickness 100 ± 20 [mu] of the photocurable resin composition
m is changed from 70% or more to 20% or less between 260 and 380 nm, and the wavelength W
1 has a parallel light transmittance of 20% or less and the wavelength W2 has a parallel light transmittance of 70% or more.

The parallel light transmittance at a thickness of 100 ± 20 μm is 50% at a wavelength W between 260 and 380 nm, and the parallel light transmittance decreases from 70% or more to 20% or less at the wavelength W. 20% parallel light transmittance at wavelength W1
Or less, preferably 10% or less, particularly preferably 5% or less, and those having a parallel light transmittance at the wavelength W2 of 70% or more, particularly preferably 80% or more are preferably used.
The wavelength W (nm) is between the wavelength W1 and the wavelength W2, particularly preferably in the range of 280 to 370 nm.

The reason why the wrinkle pattern is formed on the surface is unknown, but a thin cured film is formed only on the surface layer.
It is presumed that volume shrinkage occurs when the inside hardens, and a wrinkle pattern is formed on the surface. Curing is formed only in the vicinity of the surface, and there must be a certain time lag between the formation of the film on the surface and the curing of the inside. Two steps were required.

In the conventional method, when an active light source having a strong continuous spectrum such as a high-pressure mercury lamp or a xenon lamp is used, it is difficult to form a cured film only on the surface, and wrinkles are formed. There were problems such as not being formed, and the size and depth of wrinkles could not be controlled. However, in the present invention, by utilizing the fact that the light transmittance of the photocurable resin composition greatly changes at a wavelength W (nm) between W1 and W2, even in one-step light irradiation, continuity is strong. Even when a light source is used, a desired wrinkle pattern can be formed.

Probably, because the light transmittance of the photocurable resin composition at the wavelength W1 on the short wavelength side is small, it is possible to absorb high-energy ultraviolet rays with high efficiency and quickly form a coating film only near the surface. As a result, a thin film is formed near the surface, and then the inside of the film is cured by relatively low-energy ultraviolet rays having a longer wavelength W2.
It is presumed that the target wrinkle pattern is formed by the light irradiation at the stage. Therefore, it is preferable that the light transmittance of the photocurable resin composition at the wavelength W1 on the short wavelength side is as low as possible, and the light transmittance at the wavelength W2 on the long wavelength side is as high as possible.

Such a photocurable resin composition is capable of adjusting the type and amount of the photopolymerizable compound and photopolymerization initiator to be used, and has an ultraviolet absorbing ability such as an ultraviolet absorber and an ultraviolet stabilizer. It can be prepared by adding a low molecular compound or a chain polymer having an ultraviolet absorbing ability.

The low molecular weight compound having an ultraviolet absorbing ability has a low light transmittance on the short wavelength side, a high light transmittance on the long wavelength side, and a wavelength region in which the light transmittance largely changes is a wavelength region of 260 to 380 nm. And particularly preferably 280 to 370 n
It is possible to select and use a compound in the wavelength range of m, such compounds, compounds commonly used as ultraviolet absorbers and ultraviolet stabilizers, for example, salicylic acid-based ultraviolet absorber, Examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and hindered amine-based ultraviolet stabilizers.

The amount of the low molecular compound having an ultraviolet absorbing ability to be used is such that a photocurable resin composition having the above-mentioned optical properties can be obtained.
It is preferably at most 10% by weight, particularly preferably at most 5% by weight, based on parts by weight. If it exceeds 10% by weight, there are problems such as deterioration of curability and impairment of mechanical properties, which is not preferable.

It is also possible to use a chain polymer having an ultraviolet absorbing ability. Such a chain polymer has a low transmittance in a short wavelength range and a high transmittance in a long wavelength range, and a wavelength range where light transmittance greatly changes is 260 to
A chain polymer having a wavelength of 380 nm, particularly preferably in the range of 280 to 270 nm, is preferably used. Examples of such a chain polymer include polysulfone polymers such as porsulfone and polyethersulfone, polymaleimide polymers, and polymaleimide polymers. Examples thereof include aromatic polyesters such as arylates, polyimide polymers, phenoxy resins, and styrene copolymers.

The photocurable resin composition of the present invention contains other components such as a lubricant such as a fluorine compound and silicone; a coloring agent such as a dye, a pigment and a fluorescent dye; an antioxidant;
A thermosetting resin such as an epoxy resin; a fungicide; an antibacterial agent; an inorganic or organic powder; a reinforcing fiber or the like can be mixed or contained in the form of a copolymer. It is also possible to use a composite such as a fiber reinforced plastic or a laminate sheet.

The method for obtaining a photocurable resin composition in which a photocrosslinkable polymerizable compound, a chain polymer, a photopolymerization initiator, and a low molecular weight compound having an ultraviolet absorbing ability to be used as required are uniformly mixed. Using a method of directly (heating) mixing the components, or using a common solvent in which the photocrosslinkable polymerizable compound and the other components of the photocurable resin composition are uniformly mixed together, the photocrosslinkable polymerizable compound and the photocurable resin composition are used. After preparing a homogeneous mixed solution of the other components of the product and a solvent, the homogeneous mixed solution is applied to a substrate or the like, and the solvent is removed by a solvent casting method to obtain a uniformly mixed photocurable resin composition. Is possible.

When a solvent is used, the solvent used is
Any solvent can be used as long as it can be removed by any method such as volatilization and extraction, but a volatile solvent is preferable. The volatile solvent preferably has a boiling point of 150 ° C. or less,
It is more preferable that the temperature is 120 ° C. or lower.

Examples of such a solvent include chlorine solvents such as methylene chloride, chloroform, trichloroethane and tetrachloroethane; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and 2-butanone; ethyl acetate; Ester solvents such as butyl acetate; ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; hydrocarbon solvents such as toluene and cyclohexane; acids such as formic acid; phenols such as chlorophenol; Liquefied gas such as; supercritical fluid such as supercritical carbon dioxide.

Although the method of removing the solvent is optional, it is preferable that the solvent is removed by volatilization. The volatilization method is also arbitrary, and may be, for example, air drying, hot air drying, infrared drying, vacuum drying, or the like.

The photocurable resin composition is formed into an arbitrary shape such as a coating film, a film (including a sheet and a ribbon), a fiber, a cast, and an impregnated material. However, the shape must be curable by actinic rays. For example, it is necessary that the thickness be such that the actinic ray can reach, and when the shaped object is covered with a clothing, the clothing needs to transmit the actinic ray to be used. The shaping method is also arbitrary, and may be, for example, coating, casting, dipping, casting, impregnation, extrusion, or the like.

When the preparation of the photocurable resin composition is a method using a solvent, shaping may be performed before, after, or simultaneously with the removal of the solvent. It may be after part removal. When the viscosity of the photocurable resin composition is high or when the shaped product is a thin material such as a coating film or a film, it is preferable to remove the solvent after the shaping.

The method for producing a resin molded product having a periodic wrinkle pattern on the surface according to the present invention comprises:
It is obtained by irradiating an actinic ray to a photocurable resin composition containing a chain polymer, a photopolymerization initiator and, if necessary, an ultraviolet absorber, to cure the photocurable resin composition.

The photocurable resin composition containing (A) the photocrosslinkable polymerizable compound and (B) the chain polymer is uniformly mixed before the irradiation with actinic light, but the (A) light is irradiated by actinic light irradiation. When the molecular weight of the cross-linkable polymerizable compound increases, the compatibility decreases. Therefore, depending on the irradiation condition of the actinic ray, (A) the cured product of the photo-crosslinkable polymerizable compound and (B) the chain polymer undergo phase separation. In the present invention, it is particularly preferable to irradiate with an actinic ray under conditions (temperature and viscosity) at which (A) the photocrosslinkable polymerizable compound and (B) the chain polymer undergo phase separation.

The irradiation conditions of the actinic ray that induces phase separation differ depending on the combination (compatibility) of the (A) photocrosslinkable polymerizable compound and (B) chain polymer used and the blending ratio. Can not be specified. In general, irradiation with actinic rays at low viscosity and high temperature induces phase separation, but in the case of highly compatible combinations, it is necessary to irradiate actinic rays at lower viscosity and higher temperature, In the case of a combination having low compatibility, phase separation is induced even at a relatively high viscosity and a relatively low temperature, and a periodic wrinkle pattern is formed.
Also, as the amount of the chain polymer increases, phase separation is induced even at a relatively high viscosity, and a periodic wrinkle pattern tends to be formed.

The actinic ray irradiation of the present invention is carried out by irradiating the actinic ray with the photocurable resin composition having a viscosity of 100,000 Pa · s or less, particularly preferably 50,000 (Pa · s) or less. Is preferably cured.
When the viscosity exceeds 100,000 Pa · s, a desirable wrinkle pattern is not formed. The minimum value of the viscosity is usually 0.001.
It is at least Pa · s, particularly preferably at least 0.01 Pa · s. If the viscosity is less than 0.001 Pa · s, the periodicity of the wrinkle pattern is undesirably reduced.

Generally, when a large amount of chain polymer is used,
Although the wrinkle pattern tends to be formed even when the viscosity is high,
When the amount of the chain polymer is small, a wrinkle pattern tends to be not obtained unless the viscosity is made lower. As a method of obtaining such a viscosity, a method of changing the irradiation temperature of the actinic ray or using a low-viscosity monofunctional photopolymerizable compound is possible.

The fact that the cured product of the photocrosslinkable polymerizable compound (A) and the chain polymer (B) are phase-separated can be confirmed by direct observation with a transmission or scanning electron microscope or measurement of the glass transition temperature. It can be known by a general method described in textbooks of polymer blends for measuring the state of intermolecular interaction by nuclear magnetic resonance absorption.

In the resin molded product of the present invention, the size and depth of wrinkles can be controlled by the irradiation temperature of actinic rays. In general, the higher the irradiation temperature, the larger the size of the wrinkles and the deeper the wrinkles tend to be. However, the wrinkle depth at which the irradiation temperature exceeds a certain temperature tends to be saturated, and this temperature varies depending on the type of resin used, the blend composition ratio, and the like. In the present invention, the irradiation temperature of the actinic ray is preferably from 0 to 250 ° C.,
0 ℃ is particularly preferred.

[0078]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to the scope of the following examples.

In the following examples, a 160 W metal halide lamp (manufactured by Eye Graphics) was used as an ultraviolet light source. The UV irradiation intensity at 365 nm was about 70 mW / cm ² . The UV irradiation time was usually 90 seconds unless otherwise specified, and the surface was exposed to air.

(Measurement of Viscosity) The viscosity of the photocurable resin composition was measured by a dynamic viscoelasticity measuring device RDS ™ manufactured by Rheometrics.
Measured using II. A parallel plate having a diameter of 25 mm was used, and the sample thickness was 1.5 mm. The frequency variance of the complex viscosity was measured, and an extrapolated value to frequency = 0 was determined to be the viscosity.

(Measurement of Light Transmittance) The parallel light transmittance of the photocurable resin composition was measured using a turbidimeter “NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. The thickness of the film was about 100 μm.

(Measurement of glass transition temperature) The glass transition temperature was measured by a dynamic viscoelasticity measurement (RS manufactured by Rheometrics Co., Ltd.).
A-II). The temperature was raised at 2 ° C. per minute, and the measurement was performed at 1 Hz. The glass transition temperature was the peak temperature of tan δ.

(Electron Microscope Observation) Scanning electron microscope (S
EM) is FE-SEM S-8 manufactured by Hitachi, Ltd.
00, TEM is JEM-20 manufactured by JEOL Ltd.
0CX, 1LM15 manufactured by Lasertec Co., Ltd. was used as a scanning laser microscope.

Example 1 As a photocrosslinkable polymerizable compound,
"New Frontier BPE-4" (ethylene oxide-modified bisphenol A diacrylate manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; hereinafter abbreviated as "BPE4") 5
g, 0.1 g of "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba-Geigy) as a photopolymerization initiator and "Udel 3703" (polysulfone, manufactured by Amuco Co .; (Abbreviated as “PSF”) 5 g of methylene chloride 50
g) to obtain a homogeneous mixed solution (1).

After the thus obtained homogeneous mixed solution (1) is applied on a glass plate, the solvent is volatilized, and the uncured, colorless and transparent coating film-like photocurable resin composition of the uniform mixed solution ( 1) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was reduced from about 90 to almost 0% at 340 to 310 nm. At a wavelength of 310 nm or less, the parallel light transmittance was almost 0%, and at a wavelength of 350 nm or more, the parallel light transmittance was 80% or more. The viscosity at 150 ° C. of the photocurable resin composition (1) is about 600.
(Pa · s).

The molar extinction coefficient of Irgacure 184 was 20 (L mol -1 cm -1) at 365 nm and 313 n.
90 (L mol -1 cm -1) at m, 12 at 302 nm
0 (L mol-1 cm-1), 6800 at 254 nm
(L mol -1 cm -1), which was almost zero at 405 nm or more. ^-1

The photocurable resin composition (1) was coated with 150
C. and irradiated with ultraviolet light with the surface open to the air. A cloudy cured coating film (about 100 μm) was obtained. The light transmittance of the cured coating film was about 30%.

When the cured coating film was observed with an optical microscope,
A periodic pattern having a correlation length of about 7 μm was observed. Furthermore,
When the surface of the cured coating film was observed using a scanning electron microscope (SEM), a wrinkle pattern having a periodicity of 7 μm having substantially the same correlation length was observed. No wrinkle pattern was observed on the substrate surface of the cured coating film. When the dispersion of the wrinkle distance was measured, the dispersion was 1 μm or less. The depth of the wrinkles measured by a scanning laser microscope is about 2.5μ.
m.

FIG. 1 shows an optical microscope photograph obtained in Example 1. The lower right scale is 50 μm. The white part in the figure is the wrinkle dent part. Transmission electron microscope (TEM)
When the cross section of the coating film was observed, a network-like phase separation structure of 50 to 80 nm was observed. In addition, the glass transition temperature (T
g) clearly appeared at 88 ° C and 148 ° C.

Comparative Example 1 Using the photocurable resin composition (1), a wavelength of 320 nm or less was cut using a glass plate having substantially the same light transmission characteristics as the photocurable resin composition (1). A cured coating film was obtained in the same manner as in Example 1 except that ultraviolet light was used. The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed.

Comparative Example 2 Using the photocurable resin composition (1), a cured coating film was formed in the same manner as in Example 1 except that the irradiation temperature for irradiating ultraviolet rays was room temperature (25 ° C.). Obtained.
The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed. The viscosity of the photocurable resin composition (1) at room temperature cannot be measured and is at least 1
00000 (Pa · s) or more. The structure of the coating film was observed by TEM, but no phase structure was observed. When the glass transition temperature of the coating film was measured by dynamic viscoelasticity measurement, only one glass transition temperature was observed at 61 ° C.,
The coating showed no phase separation.

Comparative Example 3 Instead of the photocurable resin composition (1), BPE4 (5 g) and Irgacure 184 (0.1 g) were used.
A cured coating film was obtained in the same manner as in Example 1 except that 1 g) was used. The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed.

Comparative Example 4 In the photocurable resin composition (1), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide “Irgacure 819” was used instead of Irgacure 184 as a photopolymerization initiator. "
A cured coating film was prepared under the same conditions as in Example 1 except that was used. The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed.

The molar extinction coefficient of Irgacure 819
Is 380 (L mol at 405 nm) ^-1 cm^-1), 36
1000 at 5 nm (L mol^-1 cm^-1), 313n
6300 (L mol^-1 cm^-1) At 302 nm
7600 (L mol^-1 cm^-1) 82 at 254 nm
00 (L mol^-1 cm^-1) And light in the low wavelength region
It is considered that wrinkle pattern was not formed due to large absorption.
available.

Comparative Example 5 In the photocurable resin composition (1), instead of Irgacure 184, 2-methyl-1- (4-methylthiophenyl) -2- was used as a photopolymerization initiator.
Morpholino propane-1-on "Irgacure 907"
A cured coating film was prepared under the same conditions as in Example 1 except that was used. The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed.

The molar extinction coefficient of Irgacure 907 is almost zero at 405 nm and 200 (Lm at 365 nm).
ol ^-1 cm ^-1 ) and 16000 at 313 nm (L mo
1 ⁻¹ cm ⁻¹ ) and 17000 (L mol ⁻¹ ) at 302 nm.
cm ⁻¹ ), 1100 at 254 nm (L mol ⁻¹ c)
m ^-1) it was.

Comparative Example 6 In the photocurable resin composition (1), 1 Irgacure 184 was used as a photopolymerization initiator.
g (20 parts by weight) to prepare a cured coating under the same conditions as in Example 1. The cured coating film surface was observed in the same manner as in Example 1, but no wrinkle pattern was observed.

Example 2 A cured coating film was obtained using the photocurable resin composition (1) in the same manner as in Example 1 except that the irradiation temperature for irradiating ultraviolet rays was 120 ° C. When the cured coating film surface was observed in the same manner as in Example 1, a wrinkle pattern having a correlation length of 3 μm and periodicity was observed. The depth of the wrinkles was about 0.2 μm, and the cured coating film was transparent. The viscosity at 120 ° C. of the photocurable resin composition (1) was about 2000 (Pa · s). When the phase structure of the coating film was observed with a TEM, a phase structure having a size of 0.1 μm or less was observed. Two distinct glass transition temperatures appeared at 85 ° C and 136 ° C.

Example 3 In the photocurable resin composition (1), 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one was used in place of Irgacure 184 as a photopolymerization initiator. A cured coating film was prepared under the same conditions as in Example 1 except that "Darocur 1173" was used. When the cured coating film surface was observed in the same manner as in Example 1, a wrinkle pattern having a correlation length of 11 μm and periodicity was observed.

The molar extinction coefficient of Darocure 1173 is 40
Nearly zero, at 365nm with 5nm 12 (L mol ^-1
cm ⁻¹ ) 90 at 313 nm (L mol ⁻¹ c
m ^-1 ), 130 (L mol ^-1 c) at 302 nm
m ^-1 ) at 254 nm, 6670 (L mol ^-1 c
m ^-1 ).

Example 4 As a photocrosslinkable polymerizable compound,
"Aromatic polyester" (Polyarylate U-Polymer U-100, manufactured by Unitika Ltd .; hereinafter abbreviated as "PAr") as 5 g of "BPE-4", 0.1 g of Irgacure 184 and a chain polymer. 5 g was dissolved in 80 g of methylene chloride to obtain a homogeneous mixed solution (2).

After the thus obtained homogeneous mixed solution (2) was applied on a glass plate, the solvent was volatilized, and the uncured colorless and transparent coating film-like photocurable resin composition of the homogeneous mixed solution ( 2) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was reduced from about 90 to almost 0% at 360 to 340 nm. At a wavelength of 340 nm or less, the parallel light transmittance was almost 0%, and at a wavelength of 360 nm or more, the parallel light transmittance was about 90%. The viscosity at 150 ° C. of the photocurable resin composition (2) is about 1000
(Pa · s).

When the coating film of the photocurable resin composition (2) was
C. and the surface was released into the air to irradiate ultraviolet rays. A cloudy cured coating film (about 80 μm) was obtained.
The light transmittance of the cured coating film was about 35%. When the surface of the cured coating film was observed using SEM, the correlation length was 5 μm.
A wrinkle pattern having a degree of periodicity was observed. No wrinkle pattern was observed on the substrate surface of the cured coating film. When the dispersion of the wrinkle distance was measured, the dispersion was 1 μm or less. The depth of the wrinkles was about 0.5 μm. When the phase structure of the coating film was observed with a TEM, a network-like phase structure of 0.1 μm or less was clearly observed.

Example 5 As a photocrosslinkable polymerizable compound,
7 g of “BPE-4”, 0.14 g of “Irgacure 184” as a photopolymerization initiator and “PS” as a chain polymer
F "3 g was dissolved in methylene chloride 50 g to obtain a homogeneous mixed solution (3). After the thus obtained homogeneous mixed solution (3) is applied on a glass plate, the solvent is volatilized, and the uncured colorless and transparent coating-like photocurable resin composition (3) of the uniform mixed solution is obtained. Obtained.

When the light transmittance of the photocurable resin composition was measured, it was found that the parallel light transmittance was about 9 at 320 to 340 nm.
It dropped from 0 to almost 0%. At a wavelength of 320 nm or less, the parallel light transmittance was almost 0%, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%. The viscosity at 150 ° C. of the photocurable resin composition (3) is about 50 (Pa).
-S). Apply the coating film of the photocurable resin composition (3) to 1
Ultraviolet rays were irradiated while keeping the temperature at 50 ° C. and releasing the surface into the air. A cloudy cured coating film (about 100 μm) was obtained. The light transmittance of the cured coating film was 10% or less.

When the surface of the cured coating film was observed using an optical microscope, a wrinkle pattern having a periodicity with a correlation length of about 12 μm was observed. When the dispersion of the wrinkle distance was measured, the dispersion was 1 μm or less. When the phase structure of the coating film was observed with a TEM, a network-like phase structure having a size of about 0.2 μm was clearly observed.

Example 6 As a photocrosslinkable polymerizable compound,
3 g of “BPE-4”, 0.06 g of “Irgacure 184” as a photopolymerization initiator, and “PS” as a chain polymer
7 g of F "was dissolved in 70 g of methylene chloride to obtain a homogeneous mixed solution (4). After the thus obtained homogeneous mixed solution (4) is applied on a glass plate, the solvent is volatilized, and the uncured, colorless and transparent coating-like photocurable resin composition (4) of the uniform mixed solution is obtained. Obtained.

When the light transmittance of the photocurable resin composition was measured, it was found that the parallel light transmittance was about 9 at 320 to 340 nm.
From 0 to almost 0%. At a wavelength of 320 nm or less, the parallel light transmittance was almost 0%, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%. The viscosity at 150 ° C. of the photocurable resin composition (4) is about 5,000.
(Pa · s)

The coating film of the photocurable resin composition (4) was
C. and the surface was released into the air to irradiate ultraviolet rays. A cloudy cured coating film (about 100 μm) was obtained. When the surface of the cured coating film was observed using an optical microscope, a wrinkle pattern having a correlation length of about 4 μm and periodicity was observed. When the dispersion of the wrinkle distance was measured, the dispersion was 1 μm or less. When the phase structure of the coating film was observed with a TEM, a network-like phase structure of about 0.1 μm was observed.

[Examples 7 and 8] In the photocurable resin composition of Example 1, "Irgacure 18" was used as the photopolymerization initiator.
A cured coating film was prepared under the same conditions as in Example 1 except that the amount of “4” was changed to 0.05 g (0.5 parts by weight, Example 7) and 0.3 g (6 parts by weight, Example 8). did.

When the surface of the cured coating film was observed using an optical microscope, periodic wrinkles were formed on the surfaces of both coating films of Examples 7 and 8. However, the correlation length was different, and was about 15 μm in Example 7 and about 2 μm in Example 8. It can be seen that the size of the wrinkle pattern can be controlled by the amount of the photopolymerization initiator. When the phase structure of the coating film was observed with a TEM, a network-like phase structure of 0.1 μm or less was observed.

Example 9 As a photocrosslinkable polymerizable compound,
5 g of “BPE-4”, 0.1 g of “Irgacure 184” as a photopolymerization initiator, and polystyrene as a chain polymer (DIC-styrene GR4500 manufactured by Dainippon Ink and Chemicals, Incorporated; hereinafter referred to as “PS”) 5 g)
Is dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (5).
I got

After the thus obtained homogeneous mixed solution (5) was applied on a glass plate, the solvent was volatilized, and the uncured, colorless and transparent coating film-like photocurable resin composition of the homogeneous mixed solution ( 5) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was reduced from about 90 to almost 0% at 330 to 290 nm. At a wavelength near 310 nm, the parallel light transmittance was 20% or less, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%.

When the coating film of the photocurable resin composition (5) was
C. and the surface was released into the air to irradiate ultraviolet rays. A cloudy cured coating film (about 100 μm) was obtained. When the cured coating film was observed with an optical microscope, a periodic pattern having a correlation length of about 10 μm was observed. When the variation of the wrinkles was measured, the variation was 1 μm or less. The wrinkle depth measured by a scanning laser microscope was about 1 μm. When the cross section of the coating film was observed with a transmission electron microscope (TEM), a network-like phase separation structure of 0.1 μm or less was observed.

Example 10 5 g of "BPE-4" as a photocrosslinkable polymerizable compound, 0.1 g of "Irgacure 184" as a photopolymerization initiator, and an aromatic polyester (Toyobo Co., Ltd.) as a chain polymer Made of Byron-20
0) 5 g was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (6).

After the thus obtained homogeneous mixed solution (6) was applied on a glass plate, the solvent was volatilized, and the uncured, colorless and transparent coating film-like photocurable resin composition of the homogeneous mixed solution ( 6) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was about 9 at 330 to 320 nm.
It dropped from 0 to almost 0%. At a wavelength of 310 nm or less, the parallel light transmittance was almost zero, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%.

When the coating film of the photocurable resin composition (6)
C. and the surface was released into the air to irradiate ultraviolet rays. A cloudy cured coating film (about 100 μm) was obtained. When the cured coating film was observed with an optical microscope, a periodic pattern having a correlation length of about 10 μm was observed. When the variation of the wrinkles was measured, the variation was 1 μm or less. The wrinkle depth measured by a scanning laser microscope was about 0.5 μm. When the cross section of the coating film was observed with a transmission electron microscope (TEM), a network-like phase separation structure of 0.1 μm or less was observed.

Example 11 As a photocrosslinkable polymerizable compound, dicyclopentanyl diacrylate (Kayarad®
-684, manufactured by Nippon Kayaku Co., Ltd .; hereinafter abbreviated as "R684". 5), 0.1 g of "Irgacure 184" as a photopolymerization initiator, and a phenoxy resin (PKHH, manufactured by Union Carbide Co., Ltd.) as a chain polymer
5 g was dissolved in 50 g of methylene chloride to obtain a homogeneous mixed solution (7).

After the thus obtained homogeneous mixed solution (7) was applied on a glass plate, the solvent was volatilized, and the uncured, colorless and transparent coating film-like photocurable resin composition of the homogeneous mixed solution ( 7) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was reduced from about 90 to almost 0% at 330 to 300 nm. At a wavelength near 310 nm, the parallel light transmittance was 10% or less, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%. The viscosity at 150 ° C. of the photocurable resin composition (7) is about 100.
(Pa · s).

The coating film of the photocurable resin composition (7) was
UV rays were irradiated while keeping the temperature at 0 ° C. and releasing the surface into the air. A cloudy cured coating film (about 100 μm) was obtained. When the surface of the cured coating film was observed using an optical microscope, a wrinkle pattern having a periodicity with a correlation length of about 5 μm was observed. When the dispersion of the wrinkle distance was measured, the dispersion was 0.5 μm or less. When the cross section of the coating film was observed with a TEM, a network-like phase separation structure of 0.1 μm or less was observed.

Example 12 As a photocrosslinkable polymerizable compound, bisphenol A epoxy diacrylate (epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.) 5
g, "Irgacure 184" as a photopolymerization initiator.
1 g and 5 g of a phenoxy resin as a chain polymer were dissolved in 60 g of methylene chloride to obtain a homogeneous mixed solution (8).

After the thus obtained homogeneous mixed solution (8) was applied on a glass plate, the solvent was volatilized, and the uncured, colorless and transparent coating film-like photocurable resin composition of the homogeneous mixed solution ( 8) was obtained. When the light transmittance of the photocurable resin composition was measured, the parallel light transmittance was about 9 at 330 to 300 nm.
From 0 to almost 0%. At a wavelength near 310 nm, the parallel light transmittance was 10% or less, and at a wavelength of 340 nm or more, the parallel light transmittance was about 90%. The viscosity at 150 ° C. of the photocurable resin composition (8) is about 2000
(Pa · s).

The coating film of the photocurable resin composition (8) was
C. and the surface was released into the air to irradiate ultraviolet rays. A cloudy cured coating film (about 100 μm) was obtained. When the surface of the cured coating film was observed using an optical microscope, a wrinkle pattern having a correlation length of about 8 μm was observed. When the dispersion of the wrinkle distance was measured, the dispersion was 1 μm or less. When the cross section of the coating film was observed with a TEM, a network-like phase separation structure of 0.1 μm or less was observed.

[0124]

INDUSTRIAL APPLICABILITY The present invention can be applied to a wide range of photopolymerizable compound compositions, and can control the structure such as the size and depth of wrinkles, so that the optical characteristics of the obtained molded product can be easily controlled. And there is little restriction on the thickness of the molded product. In addition, it is excellent in various design properties such as a molded article having a matte (non-reflective) surface while having high transparency, and a formed article in which the inside of the coating film is transparent but the surface portion is uniformly clouded while having high transparency. Provided is a method for producing a resin molded product having a periodic wrinkle pattern on the surface.

[Brief description of the drawings]

FIG. 1 is an optical microscope photograph of a resin molded product having a periodic wrinkle pattern on the surface of the present invention, obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 4/00 C09D 4/00 5/00 5/00 Z 5/28 5/28 201/00 201/00 F-term (reference) 4D075 BB42Z BB46Z BB92Z BB93Z BB94Z BB96Z CB02 CB03 CB06 CB21 DA04 DA06 DA23 DB13 DB20 DC01 DC11 DC18 DC21 DC24 DC27 DC38 EA07 EA10 EA21 EB07 EB12 EB23 EB19 EB19 EB19 EC37 EC54 4F073 AA06 BA18 BA19 BA27 BA32. DK011 DK012 FA091 FA092 FA111 FA112 FA121 FA122 FA131 FA132 FA151 FA152 FA171 FA172 FA231 FA232 FA251 FA252 FA271 FA272 FA281 FA282 KA03 NA01 PA17 PC08

Claims (6)

[Claims] (A) a photocrosslinkable polymerizable compound, (B) a chain polymer, and (C) two wavelengths W1 and W2 (250 nm).
<W1 <W2 <410 nm), exhibiting light absorption, W1 having a molar extinction coefficient of 3000 (L · mol ⁻¹ · cm ⁻¹ ) or more, and W2 having a molar absorption coefficient of 150 to 5 (L · mol ⁻¹ · c).
m- ¹ ) to a photocurable resin composition containing a photopolymerization initiator having a molar extinction coefficient of 100,000 P
At a temperature of not more than a · s, the composition is irradiated with an actinic ray having a light intensity of 10 mW / cm ² or more at wavelengths W1 and W2, and the composition is cured in one step. Method for producing a resin molded article having 2. The mixing weight ratio of (A) the photocrosslinkable polymerizable compound and (B) the chain polymer is (A) :( B) = (90: 1).
0) to (20:80). 3. The resin-forming product according to claim 1, wherein (C) 15 parts by weight or less of a photopolymerization initiator is used based on 100 parts by weight of the photocrosslinkable polymerizable compound. Manufacturing method. 4. The wavelengths W1 and W2 of 250 nm <250 nm.
Thickness 100 of the photocurable resin composition containing a photopolymerization initiator satisfying W1 <310 nm and 350 nm <W2 <410 nm
The parallel light transmittance of ± 20 μm decreases from 70% or more to 20% or less at a wavelength W (nm) between 260 and 380 nm, and the parallel light transmittance at the wavelength W1 is 20% or less. The method according to any one of claims 1 to 3, wherein a parallel light transmittance at a wavelength W2 is 70% or more. 5. The method according to claim 4, wherein a photoinitiator having a molar extinction coefficient of 1000 (L · mol ⁻¹ · cm ⁻¹ ) or less in a wavelength range of wavelength W (nm) to 500 nm is used. The method for producing the resin formed product according to the above. 6. The method according to claim 1, wherein (B) the chain polymer is at least one member selected from the group consisting of a polysulfone polymer, an aromatic polyester polymer, a styrene copolymer, and a phenoxy resin. A method for producing the resin formed product according to any one of the above.