JP2019001138A - Molding jig and manufacturing method of cured product of photocurable resin - Google Patents

Abstract

To provide a technology, capable of suppressing problems due to volume decrease caused by hardening shrinkage of a photocurable resin.SOLUTION: The molding jig contains a spacer having a center space and an inlet, an upper face member, a lower face member, and a connection member, wherein the upper face member and the lower face member is composed of a transparent plate transmitting an active light and a light-shielding member attached to one face of the transparent plate, the light-shielding member has a central part which contains a transmission port provided as a notch of the light-shielding member, and the center space is composed of a light-shielding part provided by covering the upper and lower surfaces with the light-shielding member and a light-transmitting part in which the upper and lower surfaces are not covered with the light-shielding member.SELECTED DRAWING: Figure 7

Description

  The present invention relates to a molding jig and a method for producing a photocurable resin cured product.

  As a technique for obtaining a molded product having a desired three-dimensional shape, a technique is known in which a liquid resin is cured with a thermosetting resin or a photocurable resin, and then the liquid resin is cured. Regardless of whether a curable resin or a photocurable resin is used, a volume reduction (hereinafter referred to as “shrunk”) may occur in a molded product molded from a liquid resin due to curing shrinkage. The close-up causes problems such as loss of aesthetics and failure to produce the intended shape and / or dimensions. In order to suppress the shrinkage, conventionally, molding is performed by blending a filler with a liquid resin.

  Although a photocurable resin has a larger curing shrinkage than a thermosetting resin, it is excellent in optical characteristics, so that there is an increasing demand for high-precision components such as optical components using the photocurable resin. However, when a large amount of filler is added to the photocurable resin, the optical properties are deteriorated. Therefore, when manufacturing optical parts using a photocurable resin, a method for suppressing the shrinkage by adding a large amount of the filler is Cannot be adopted.

  As a technique for suppressing the above-mentioned problems caused by photocuring resin shrinkage (problems such as loss of aesthetics or inability to obtain the intended shape and dimensions), Patent Document 1 discloses a resin holding via a resin supply valve. After filling the space with a photocurable resin, light is irradiated from the light source to cure the photocurable resin in the resin holding space to obtain a molded body. Before the photocurable resin in the resin holding space is completely cured, the protruding pin is pressed against the photocurable resin in the resin holding space to form a recess, that is, the resin is held by forming the recess. Even if the shrinkage, which is a volume reduction due to curing shrinkage, occurs by pressing the photocurable resin in the space and forming the photocurable resin along the resin holding space, the shape of the molded product To the resin holding space Possible and a technique that the intended shape to have been disclosed.

JP 2011-25606 A

The technique of Patent Document 1 is to form a cured product of a photocurable resin on the surface of an object such as a resin plate or a metal plate, and a resin holding space filled with the photocurable resin via a resin supply valve is The object, a light guide type (transparent mold) that transmits light, and a resin supply valve with a protruding pin are included. In this method, if there is a slight leak in the resin holding space, the pressure due to the protrusion of the protruding pin is not sufficiently transmitted to the photocurable resin in the resin holding space, and the shape of the molded product is intended to correspond to the resin holding space. There was a problem of not being in shape.
Moreover, although the technique of patent document 1 presupposes using the comparatively low molecular weight photocurable resin which shows fluidity at normal temperature, such a photocurable resin is resin holding | maintenance at the time of protrusion of a protrusion pin. It tends to leak from space. In order to avoid this phenomenon, if the photocurable resin in the resin holding space is cured to some extent and the viscosity is increased, and then the protruding pin is protruded, the pressure is not uniformly transmitted through the photocurable resin, but partially. There is a problem that the shrinkage occurs and the shape of the molded product does not become the intended shape corresponding to the resin holding space.
Furthermore, in the method of Patent Document 1, it is necessary to produce a transparent mold each time according to the shape of a desired molded product, and the cost burden is large, so there is a problem that it is not suitable for small-scale production or trial production. there were.

  The present invention solves the above-mentioned problems, and when a mold is filled with a photocurable resin and cured to obtain a molded product, problems caused by shrinkage (damage to aesthetics, or the intended shape and dimensions cannot be obtained) It is possible to provide a technology that can suppress the above problem) and can suppress the manufacturing cost of the mold.

In order to solve the above problems, the present inventors have intensively studied. As a result, they have found that the above problems can be solved by using a molding jig having a specific structure, and completed the present invention. The present invention provides the following [1] to [4].
[1] A spacer having a central space formed in the central portion of the plate-like member, and an injection port connecting the central space and the outer edge of the plate-like member;
An upper surface member disposed on the upper surface of the spacer and covering the upper surface of the central space;
A lower surface member disposed on the lower surface of the spacer and covering the lower surface of the central space;
A molding jig comprising a connecting member that penetrates and fixes the spacer, the upper surface member, and the lower surface member,
The upper surface member and the lower surface member are composed of a transparent plate that transmits actinic rays and a light-shielding member attached to one surface of the transparent plate,
The light shielding member has a transmission port formed by cutting out the light shielding member at a central portion,
A molding jig, wherein the central space includes a light shielding portion whose upper and lower surfaces are covered with the light shielding member, and a light transmitting portion whose upper and lower surfaces are not covered with the light shielding member.
[2] The forming jig according to [1], wherein the light shielding member is a light shielding tape including an adhesive tape on one side.
[3] A method for producing a photocurable resin cured product, wherein the photocurable resin cured product is molded using the molding jig according to [1],
A filling step of injecting a photocurable resin from the injection port and filling the central space with the photocurable resin;
A method for producing a photocurable resin cured product, comprising an irradiation step of irradiating an actinic ray toward the forming jig and transmitting the actinic ray to the translucent part.
[4] In the irradiation step, the volume of the photocurable resin reduced by photocuring shrinkage is uncured in the light-shielding portion and / or in the injection port in the light-shielding portion and uncured. The method for producing a cured photocurable resin according to [3], which is supplemented with a photocurable resin.

  When the photocurable resin cured product is molded using the molding jig having the configuration of the above [1], when the active ray is irradiated, the volume of the photocurable resin is reduced due to photocuring shrinkage. Since it is supplemented with an uncured resin in the light-shielding portion and / or an uncured photocurable resin in the injection port, it can suppress problems caused by shrinkage due to curing shrinkage of the photocurable resin. it can. In addition, the presence of the uncured resin can prevent the occurrence of cracks due to the difference in the linear expansion coefficient between the spacer and the photocurable resin.

  The molding jig having the simple structure [1] can be obtained at a lower cost than conventional transparent molds, and can be suitably used for a small amount of production or trial production.

It is a whole perspective view of the forming jig in one embodiment. It is a vertical sectional view of a forming jig in one embodiment. It is a top view of the forming jig in one embodiment. It is a top view of the spacer in one Embodiment. It is a top view of the upper surface member in one embodiment. It is a top view of the lower surface member in one embodiment. It is a vertical sectional view of a forming jig in one embodiment, and is a figure explaining the state where actinic rays were irradiated.

  Hereinafter, the manufacturing method of the shaping | molding jig and photocurable resin hardened | cured material in one Embodiment of this invention is explained in full detail. In addition, this invention is not made into the following embodiment.

[Molding jig]
As shown in FIGS. 1 and 2, the forming jig includes a plate-like spacer 1, an upper surface member 2 disposed on the upper surface of the spacer 1, a lower surface member 3 disposed on the lower surface of the spacer 1, and the spacer 1. And a connecting member 4 that penetrates and fixes the upper surface member 2 and the lower surface member 3.
The connecting member 4 is a cylindrical member having a function of aligning and fixing the spacer 1, the upper surface member 2, and the lower surface member 3. Examples of the connecting member 4 include a pin made of stainless steel or iron.

The spacer 1 is composed of a plate-like member having a uniform thickness, and has a central space 5 at the center as shown in FIG. The central space 5 can be formed by hollowing out the plate member having the uniform thickness into a desired shape.
The spacer 1 also has an injection port 6 for injecting a photocurable resin into the central space 5. The injection port 6 can be formed by cutting out the plate member so as to connect the central space 5 and the outer edge of the plate member.
The spacer 1 has a connecting hole 7 into which the connecting member 4 is inserted.
Examples of the material of the spacer 1 include aluminum, stainless steel, iron, plastic, and rubber.

As shown in FIG. 5, the upper surface member 2 includes a transparent plate 8 that transmits actinic rays and a light shielding member 9 attached to the upper surface of the transparent plate 8. The light shielding member 9 has the light shielding member in the center. It has a transmission port 10 formed by cutting out the member 9.
The transparent plate 8 and the light shielding member 9 have a connection hole 11 into which the connection member 4 is inserted.

As shown in FIG. 6, the lower surface member 3 includes a transparent plate 12 that transmits actinic rays and a light shielding member 13 attached to the lower surface of the transparent plate 12. The light shielding member 13 has the light shielding member at the center. It has a transmission port 14 formed by cutting out the member 13.
The transparent plate 12 and the light shielding member 13 have a connection hole 15 into which the connection member 4 is inserted.

The transparent plates 8 and 12 are transparent plates that transmit actinic rays necessary for curing the photocurable resin. Examples of the transparent plates 8 and 12 include glass and plastic.
A material that does not absorb the wavelength of the active light to be used is desirable. Quartz glass is particularly preferred, but polyolefin resins such as acrylic resin and polyethylene resin can also be used.

  The light shielding members 9 and 13 are members having a function of blocking actinic rays. Examples of the light shielding members 9 and 13 include a light shielding tape having an adhesive tape on one side.

  The opening area (S1) of the transmission port 10 of the upper surface member 2 and the opening area (S2) of the central space 5 of the spacer 1 are similar and have a relationship of S1 <S2. The opening area (S1 ′) of the transmission port 14 of the lower surface member 3 and the opening area (S2) of the central space 5 of the spacer 1 are also similar and have a relationship of S1 ′ <S2. For this reason, as shown in FIG. 7, the central space 5 of the spacer 1 has a light shielding portion 16 whose upper and lower surfaces are covered with light shielding members 9 and 13, and a light transmitting portion 17 whose upper and lower surfaces are not covered with the light shielding member.

  The forming jig sandwiches the spacer 1 between the transparent plate 8 of the upper surface member 2 and the transparent plate 12 of the lower surface member 3, and connects the connection hole 11 of the upper surface member 2, the connection hole 7 of the spacer 1, and the lower surface member 3. The hole 15 can be aligned and the connecting member 4 can be inserted and fixed for assembly.

[Method for producing cured photocurable resin]
In the method for producing a cured photocurable resin in the present embodiment, a liquid or softened photocurable resin is injected from the injection port 6 of the forming jig, and the photocurable resin is injected into the central space 5 of the spacer 1. As shown in FIG. 7, the filling step for filling and the irradiation step of irradiating the forming beam with the actinic ray 18 and transmitting the actinic ray to the light transmitting portion 17 of the spacer 1 are provided. After the photocurable resin is cured, the molding jig is disassembled to take out the cured photocurable resin that is a molded product.

In the irradiation step, actinic rays are irradiated to the photocurable resin through the light transmitting portion 17 of the spacer 1. When the photocurable resin is irradiated with actinic rays, the volume of the photocurable resin is reduced due to photocuring shrinkage. However, according to the method of the present invention, the photocurable resin is uncured and has fluidity in the light shielding portion 16. The resin and / or the photocurable resin that is in the injection port 6 and is uncured and has fluidity, is supplemented by the volume decrease of the photocurable resin due to photocuring shrinkage.
For this reason, according to this invention, the problem resulting from the shrinkage | contraction of photocurable resin can be suppressed. In addition, the presence of the uncured resin having fluidity can prevent the occurrence of cracks due to the difference in linear expansion coefficient between the spacer and the photocurable resin.

  Hereinafter, processing conditions, resins, and the like used in the method for producing a photocurable resin cured product according to the present embodiment will be described in detail.

(Active light)
The actinic rays are generally electron beams and ultraviolet rays, but are not particularly limited. For example, ultraviolet rays (about 380 to 450 nm), visible rays (about 620 to 750 nm), laser beams, and the like can be used as the light rays having a wavelength that promotes the reaction of the photoreactive material contained in the photocurable resin. For example, a cured product can be obtained by irradiating an uncured photocurable resin with a certain amount of ultraviolet rays (UV) using an ultraviolet exposure device and curing the photocurable resin. Examples of the ultraviolet exposure apparatus include sunlight, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a semiconductor laser.

(Photo-curing resin)
A photocurable resin is a synthetic organic material that changes from a liquid state to a solid state under the action of light energy, and is generally composed of a polymerizable compound, an oligomer and / or polymer thereof, a photopolymerization initiator, and various additives. It is.
Curing shrinkage is said to reduce the volume as a result of the reaction of the compounds constituting the composition and the rearrangement of the arrangement thereof, and it is said that the polymerizable compound having a double bond contributes greatly. Curing shrinkage can be suppressed by reacting a polymerizable compound in advance and shrinking it as an oligomer and / or polymer and reducing the amount of the polymerizable compound.
The oligomer and / or polymer is preferably in a liquid state and has a functional group so that it can be cured alone or in combination with a polymerizable compound.
It is preferable that a photocurable resin contains the following (A) component, (B) component, and (C) component.

[(A) component: a polymer having a (meth) acryloyl group in the side chain]
Examples of the component (A) include an acrylic polymer (a1) having a side chain modified with a (meth) acryloyl group, an isoprene polymer (a2) having a side chain modified with a (meth) acryloyl group, and the like.
The acrylic polymer (a1) whose side chain is modified with a (meth) acryloyl group preferably has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). As a method of modifying the side chain by (meth) acryl, for example, a structural unit having a hydroxyl group represented by the following general formula (3) or a structural unit having a carboxyl group is allowed to have in the main chain of the polymer, There is a method of adding a (meth) acrylate having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate represented by the following general formula (4). Further, as another method, for example, there is a method in which a structural unit having a glycidyl group as represented by the following general formula (5) is provided in the main chain of the polymer and (meth) acrylic acid is added thereto. Can be mentioned. Furthermore, although the method of forming a (meth) acryl side chain by graft polymerization is also mentioned, it has isocyanate groups, such as 2-isocyanatoethyl (meth) acrylate, in the hydroxyl group as shown by following General formula (3) ( A method of adding (meth) acrylate or a method of adding (meth) acrylic acid to a glycidyl group as shown by the following general formula (5) is more preferable.
When a (meth) acrylate having an isocyanate group is added to a hydroxyl group represented by the following general formula (3), the (meth) acrylate having an isocyanate group is added in an amount of 0.01 to 0. It is preferable to add such that the ratio is 9 equivalents. Similarly, when (meth) acrylic acid is added to a glycidyl group as represented by the following general formula (5), a ratio of 0.01 to 0.9 equivalent of (meth) acrylic acid to 1 equivalent of glycidyl group It is preferable to add such that
According to these methods, a structure in which a side chain (meth) acryloyl group is bonded to the main chain via a urethane bond or an ester bond is obtained. These structures are preferable from the viewpoints of impact absorption, low dielectric constant and the like.

(In General Formulas (1) and (2), R ^1A , R ^2A and R ^2B each independently represent hydrogen or a methyl group, and R ^1B represents an alkyl group or alicyclic alkyl group having 4 to 18 carbon atoms. X represents —CH ₂ CH ₂ —, — (CH ₂ CH ₂ O) pCH ₂ CH ₂ — {p is an integer of 1 to 500}, —R ^2C —OCONH—R ^2D — or R ^2E —CH. (OH) CH ₂ — is represented, and R ^2C , R ^2D and R ^2E each independently represent an alkylene group having 1 to 10 carbon atoms or an alicyclic alkylene group.

(In General Formula (3), R ^3A represents hydrogen or a methyl group, and R ^3B represents an alkylene group having 1 to 10 carbon atoms or an alicyclic alkylene group.)

(In General Formula (4), R ^4A represents hydrogen or a methyl group, and R ^4B represents an alkylene group having 1 to 10 carbon atoms or an alicyclic alkylene group.)

(In General Formula (5), R ^5A represents hydrogen or a methyl group, and R ^5B represents an alkylene group having 1 to 10 carbon atoms or an alicyclic alkylene group.)

In the acrylic polymer (a1) in which the side chain is modified with a (meth) acryloyl group, it is preferable that the general formula (1) is mainly included.
R ^1B is preferably an alkyl group having 8 to 12 carbon atoms.

  On the other hand, examples of the isoprene polymer having the (a2) (meth) acryloyl group include compounds represented by the following general formula (6).

(In General Formula (6), m represents a number of 50 to 1000, n represents a number of 1 to 5, and R ^6A represents a hydrogen atom or a methyl group.)
m is preferably 100 to 800, more preferably 150 to 700, and still more preferably 200 to 600. n is preferably 1.5 to 4, more preferably 1.5 to 3.5, and still more preferably 1.5 to 3.

  The compound represented by the general formula (6) is commercially available as UC102 and UC203 (manufactured by Kuraray Co., Ltd.).

  From the viewpoint of suppressing curing shrinkage, it is preferable to use (a1) and (a2) in combination.

Specifically, the weight average molecular weight of the component (A) is preferably 3,000 to 300,000, more preferably 5,000 to 100,000, and still more preferably 9,000 to 50,000.
In the present embodiment, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

  60-100 mass% is preferable with respect to the total amount of (A) component and (B) component, and, as for content of (A) component, 73-100 mass% is more preferable, and 80-100 mass% is still more preferable. When it is 60% by mass or more, the curing shrinkage rate is reduced.

[(B) component: polymerizable compound]
Examples of the component (B) include a monomer (b1) having one (meth) acryloyl group in the molecule, a monomer (b2) having two or more (meth) acryloyl groups in the molecule, and the like. Is mentioned.

(Monomer (b1) having one (meth) acryloyl group in the molecule)
As the monomer (b1) having one ethylenically unsaturated group in the molecule, acrylic acid, methacrylic acid, and derivatives thereof (hereinafter sometimes referred to as (meth) acrylic acid derivatives) are preferable. Can be mentioned.

Specifically, as the monomer (b1) having one ethylenically unsaturated group in the molecule, methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylate, isononyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and aralkyl (meth) acrylates such as benzyl (meth) acrylate , Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate, aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid esters of diethylene glycol ethyl ether, tri (Meth) acrylic acid ester of polyalkylene glycol alkyl ether such as (meth) acrylic acid ester of tylene glycol butyl ether, (meth) acrylic acid ester of dipropylene glycol methyl ether, (meth) acrylic acid ester of hexaethylene glycol phenyl ether (Meth) acrylic acid esters of alkylphenoxypolyethylene glycols having 4 to 12 carbon atoms such as (meth) acrylic acid esters of polyalkylene glycol aryl ethers, and (meth) acrylic acid esters of nonylphenoxypolyethylene glycol The average value of ethylene glycol structural units is 1 to 20), cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate , (Meth) acrylic acid ester having an alicyclic group such as methoxylated cyclodecatriene (meth) acrylate, fluorinated alkyl (meth) acrylate such as heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate and other hydroxyl group-containing (meth) acrylic acid esters, glycidyl (meth) acrylate and other glycidyl groups (Meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylamide, (meth) acryloylmorpholine, etc. are mentioned. From the viewpoint of further reducing the curing shrinkage rate, an alkylphenoxypolyethylene glycol (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms (average of ethylene glycol structural units is 1 to 20) is preferable.
The monomer (b1) having one ethylenically unsaturated group in these molecules can be used alone or in combination of two or more.
In addition to or instead of the above (meth) acrylic acid derivative, use a monomer having one ethylenically unsaturated bond in the molecule such as (meth) acrylonitrile, styrene, vinyl acetate, ethylene, propylene. However, (meth) acrylic acid derivatives are preferred.

(Monomer (b2) having two or more ethylenically unsaturated groups in the molecule)
The monomer (b2) having two or more ethylenically unsaturated bonds in the molecule can be used together with the monomer (b1) having one ethylenically unsaturated group in the molecule.

  When using the monomer (b2) having two or more ethylenically unsaturated groups in the molecule, two or more in the molecule in the component (B) from the viewpoints of curability, adhesion and curing shrinkage. The content of the monomer (b2) having an ethylenically unsaturated group is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 10 mass%, still more preferably from 1 to 5 mass%.

  As the monomer (b2) having two or more ethylenically unsaturated groups in the molecule, as in the case of the monomer (b1) having one ethylenically unsaturated group in the molecule, acrylic acid is used. , Methacrylic acid, and derivatives thereof ((meth) acrylic acid derivatives) are preferred.

  Examples of the monomer (b2) having two or more ethylenically unsaturated bonds in the molecule include bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3- Butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

  As the monomer (b2) having two or more ethylenically unsaturated bonds in the molecule, a diacrylate of an alkylene oxide adduct of bisphenol A represented by the following general formula (7), a general formula (8 ) Epichlorohydrin modified product of bisphenol A and acrylic acid addition ester product, diacrylate of alkylene oxide adduct of phosphoric acid represented by general formula (9), and epichlorohydrin modification of phthalic acid represented by general formula (10) Product and acrylic acid addition esterified product, 1,6-hexanediol epichlorohydrin modified product of general formula (11) and acrylic acid addition esterified product (having two acrylic groups in one molecule), general formula Triacrylate of an alkylene oxide adduct of phosphoric acid represented by (12), represented by general formula (13) Triacrylates of the alkylene oxide adduct of trimethylol propane that.

(However, in General formula (7), R < ^7A > and R < ^7B > show an ethylene group or a propylene group each independently, m and n show the integer of 1-5 each independently, m and n are each 2 In the above case, a plurality of R ^7A —O may be the same or different, and a plurality of R ^7B —O may be the same or different.)

(In the general formula (8), a and b each represent 1)

(In the general formula (9), R ^9A and R ^9B each independently represent an ethylene group or a propylene group, c and d each independently represent an integer of 1 to 5, and c and d are each 2) In the above case, a plurality of R ^9A —O may be the same or different, and a plurality of R ^9B —O may be the same or different.)

(In the general formula (10), e and f each represent 1)

(However, in general formula (11), g and h show 1)

(However, in general formula (12), R ^<12A > shows an ethylene group or a propylene group, and three i show an integer of 1-5 each independently, and when i is two or more, several R ^<12A >- O may be the same or different.)

(In the general formula (13), R ^13A , R ^13B and R ^13C each independently represent an ethylene group or a propylene group, j, k and p each independently represent an integer of 1 to 3; j , K and p are each 2 or more, the plurality of R ^13A —O, R ^13B —O and R ^13C —O may be the same or different from each other.)

In addition to or in place of the above (meth) acrylic acid derivative, a monomer (divinylbenzene or the like) having two or more other ethylenically unsaturated bonds in the molecule can also be used. ) Acrylic acid derivatives are preferred.
The monomer (b2) having two or more ethylenically unsaturated bonds in these molecules can be used alone or in combination of two or more.

  Moreover, what contains the compound which has a 2 or more epoxy group in a molecule | numerator as a preferable polymeric compound other than the said (meth) acrylate is mentioned.

Specifically, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy Resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, etc. bifunctional phenol glycidyl ether type epoxy resin; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated 2,2'- Hydrogenated bifunctional phenol glycidyl ether type epoxy resin such as biphenol type epoxy resin, hydrogenated 4,4'-biphenol type epoxy resin; phenol novolac type epoxy resin, cresol novolac Polyfunctional phenol glycidyl ether type epoxy resins such as epoxy resin, dicyclopentadiene-phenol type epoxy resin, dicyclopentadiene-cresol type epoxy resin, tetraphenylolethane type epoxy resin, etc .; polyethylene glycol type epoxy resin , Polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, 1,6-hexanediol type epoxy resin, etc. bifunctional aliphatic alcohol glycidyl ether type epoxy resin; cyclohexanediol type epoxy resin, cyclohexanedimethanol type epoxy resin, tri Bifunctional alicyclic alcohol glycidyl ether type epoxy resin such as cyclodecane dimethanol type epoxy resin; Trimethylolpropane type epoxy resin, sorbitol type Trifunctional or higher polyfunctional aliphatic alcohol glycidyl ether type epoxy resin such as poxy resin and glycerin type epoxy resin; Bifunctional aromatic glycidyl ester such as diglycidyl phthalate; Tetrahydrophthalic acid diglycidyl ester, Hexahydrophthalic acid di Bifunctional alicyclic glycidyl esters such as glycidyl ester; bifunctional aromatic glycidyl amines such as N, N-diglycidyl aniline and N, N-diglycidyl trifluoromethylaniline; N, N, N ′, N′-tetra Trifunctional or higher polyfunctional aromatic glycidylamine such as glycidyl-4,4-diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, o-triglycidyl-p-aminophenol An alicyclic diepoxy acetal, Bifunctional cycloaliphatic epoxy resins such as cyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinylcyclohexene dioxide; 1,2-epoxy-4- of 2,2-bis (hydroxymethyl) -1-butanol Trifunctional or higher polyfunctional alicyclic epoxy resin such as (2-oxiranyl) cyclohexane adduct; Trifunctional or higher functional heterocyclic epoxy resin such as triglycidyl isocyanurate; Silicon-containing organopolysiloxane type epoxy resin A bifunctional or trifunctional or higher polyfunctional epoxy resin is exemplified.
Among these, from the viewpoint of transparency and heat resistance, the above bifunctional phenol glycidyl ether type epoxy resin; the above hydrogenated bifunctional phenol glycidyl ether type epoxy resin; the above trifunctional or more polyfunctional phenol glycidyl ether type epoxy resin; A bifunctional alicyclic alcohol glycidyl ether type epoxy resin is preferred.
These compounds can be used alone or in combination of two or more, and can also be used in combination with other polymerizable compounds.

[(C) component: photopolymerization initiator]
The component (C) is not particularly limited as long as it initiates polymerization by irradiation with actinic rays such as ultraviolet rays. For example, when a compound having an ethylenically unsaturated group is used as the component (B), radical photopolymerization is initiated. Agents and the like.

There is no restriction | limiting in particular as radical photopolymerization initiator, benzoin ketals, such as 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4 [4- ( Α-hydroxy ketones such as 2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyethoxy) oxyphenylacetate Ethyl, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl oxyphenylacetate Of 2-benzyl-2-dimethylamino-1- (4-morpholin-4-ylphenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropan-1-one Α-amino ketones such as 1,2-octanedione, 1- [4- (phenylthio), 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl], 1- (O-acetyloxime) and other oxime esters; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentylphosphine oxide, phosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 2,4,5-triarylimidazole dimers such as 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N′-tetramethyl -4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophene Non-benzophenone compounds such as 4-methoxy-4'-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3 -Quinone compounds such as dimethyl anthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin ; Benzyl compounds such as benzyl dimethyl ketal; 9-phenyl acridine, 1,7-bis (9,9'-acridinyl heptane) or the like of acridine compounds: N- phenylglycine, coumarin and the like.
In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may give the same and symmetric compounds, but give differently asymmetric compounds. May be.
The above radical photopolymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  Moreover, when using said epoxy resin as (C) polymeric compound, a photocationic polymerization initiator etc. are mentioned as a photoinitiator.

  As a photocationic polymerization initiator, aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate; diaryliodonium salts such as diphenyliodonium hexafluorophosphate and diphenyliodonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexa Triarylsulfonium salts such as fluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate; Phenylselenonium hexafluoro Triarylselenonium salts such as sulfate, triphenylselenonium tetrafluoroborate and triphenylselenonium hexafluoroantimonate; dialkylphenacylsulfonium salts such as dimethylphenacylsulfonium hexafluoroantimonate and diethylphenacylsulfonium hexafluoroantimonate Dialkyl-4-hydroxy salts such as 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate; α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate, α-sulfo Examples thereof include sulfonic acid esters such as nitroxy ketone and β-sulfonyloxy ketone.

  Among these, the above triarylsulfonium salts are preferable from the viewpoints of curability, transparency, and heat resistance. These thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  (C) It is preferable that the compounding quantity of a component is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. If it is 0.1 parts by mass or more, curing is sufficient, and if it is 10 parts by mass or less, sufficient light transmittance is obtained. From the above viewpoint, the blending amount of the polymerization initiator is more preferably 0.3 to 7 parts by mass, and further preferably 0.5 to 5 parts by mass.

  In addition to these, various additives may be contained as required, such as adhesion improvers such as silane coupling agents, hindered amine light stabilizers, phenolic and phosphorus antioxidants, curing accelerators. Agents, chain transfer agents such as thiol compounds, dyes, fillers, pigments, thixotropic agents, plasticizers, flame retardants, mold release agents, surfactants, lubricants, antistatic agents, various fillers, heavy metal deactivators, etc. Additives can be added. These may be used individually by 1 type and may use 2 or more types together.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Production of materials]
(Photo-curing resin)
[(A) Synthesis of polymer having (meth) acryloyl group in side chain]
In a reaction tube, 99 g of lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 1 g of hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.), 0.75 g of n-octyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and perbutyl O (t-butyl par) 0.5 g of oxy-2-ethylhexanoate (manufactured by NOF Corporation) was added, and after stirring, placed in an 80 ° C. water bath and heated for 4 hours. Subsequently, after hold | maintaining in 100 degreeC oven for 1 hour, it removed from oven and left until it became room temperature (about 25 degreeC). Next, 0.051 g of methyl ether hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.08 g of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko KK) were added. The reaction tube was heated in a bath at 60 ° C. for 3 hours to obtain the target acrylic polymer 1 (weight average molecular weight of about 10,000).

(Photocurable resin 1)
(A) 55 parts by mass of the above acrylic polymer 1 as a polymer having a (meth) acryloyl group in the side chain, isoprene UC-102 having a methacryloyl group (made by Kuraray Co., Ltd., having the structure represented by the general formula (6) M = 400, n = 2, number average molecular weight 17,000) 20 parts by mass, (B) 20 parts by mass of light acrylate LA (lauryl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) as the polymerizable compound, (C) Irgacure 1870 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and 1-hydroxy-cyclohexyl-phenyl-ketone mixture, BASF Corporation, “Irgacure” as a photopolymerization initiator Is a registered trademark.) 1 part by mass, spherical particles (cross-linked polymethyl methacrylate, Techpolymer S) X-6, Sekisui Plastics Co., Ltd.) was mixed with the photocurable resin 1 1.05 part by weight.

(Photocurable resin 2)
(B) 100 parts by mass of DCP-A (dicyclopentadiene dimethanol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) as the polymerizable compound, (C) Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone) as the photopolymerization initiator , BASF) and spherical particles (cross-linked polymethyl methacrylate, Techpolymer SBX-6, manufactured by Sekisui Plastics Co., Ltd.) (1.0 part by mass) were mixed to obtain photocurable resin 2.

[Production of cured photocurable resin (molded product)]
As a photo-cured resin cured product, a sheet-shaped molded product (light scattering component) having a length of 40 mm, a width of 40 mm, and a thickness of 1.05 mm was produced as follows.
Example 1
A 3 mm thick blue plate glass cut into 90 mm × 90 mm and 90 mm × 70 mm was prepared one by one, and a pin insertion hole was processed. A light-shielding Kapton tape having a width of 200 mm was prepared, punched with a blade mold prepared in advance with a predetermined size, and attached to the blue plate glass while being aligned with a φ3.0 mm pin. As the spacer, SUS430 having a thickness of 1.05 mm was prepared and cut into a predetermined size by wire cutting.
Next, after stacking the lower blue plate glass, the spacer, and the upper blue plate glass in this order, alignment and fixing were performed with pins to produce the forming jig shown in FIG. Pouring a photocurable resin from the resin injection port of the mandrel, 25 mJ / cm 2 from the upper surface by ultraviolet exposure apparatus having a high-pressure mercury lamp ^were irradiated by molding the ultraviolet light of 65 mJ / cm ² from the lower surface. Thereafter, the molded product was removed from the molding jig, and the following evaluation was performed.
(Comparative Example 1)
A molded product was produced in the same manner as in Example 1 except that a spacer having no inlet was used and the resin injection method was changed. In Comparative Example 1, the resin was injected in a state where the spacer was placed on the lower surface jig provided with the light shielding tape on the blue plate glass, and the upper surface jig provided with the light shielding tape was placed on the blue plate glass for alignment. .
(Comparative Example 2)
A molded product was produced in the same manner as in Example 1 except that the light-shielding film was not applied.
(Comparative Example 3)
A molded product was produced in the same manner as in Example 1 except that no positioning pin was used.

[Evaluation]
About Example 1 and Comparative Examples 1-3, the workability | operativity in the hardening process of a photocurable hardened | cured material was evaluated. Moreover, the external appearance observation after hardening was performed and the completed said photocurable hardened | cured material was evaluated. The evaluation results are shown in Table 1.
In the following table, the evaluation was performed according to the following criteria, and evaluations were made with ○ indicating that the criteria were satisfied and × indicating that the criteria were not satisfied.
(Workability)
Resin fillability: No visible voids and / or unfilled parts in the resin filled inside the spacer.
Positionability: The amount of positional deviation with respect to the glass provided with the spacer and the light-shielding tape is ± 1.0 mm or less.
(appearance)
Cracks: No cracks and / or visible cracks after molding.
Surface irregularities: No irregularities visible on the surface after molding.
Thickness unevenness: The thickness variation after molding is ± 50 μm with respect to the design value.

Example 1
In the examples using the molding jig of the present invention, workability was good, and the appearance of the completed previous photo-cured cured product was good with no cracks, surface irregularities, thickness irregularities and the like.
(Comparative Example 1)
In Comparative Example 1 using a molding jig in which the resin injection port was not provided in the spacer, the workability was poor and the central space in the spacer could not be filled with the resin. In addition, the resin was insufficiently replenished against the shrinkage that occurred during photocuring, and cracks, surface irregularities, and uneven thickness were observed.
(Comparative Example 2)
In Comparative Example 2 using a molding jig without a light-shielding film, the resin on the side surface inside the inlet and the spacer is also cured at the time of photocuring, so the resin is not replenished for the shrinkage that occurs at the time of photocuring. Cracks, surface irregularities, and uneven thickness were observed.
(Comparative Example 3)
In Comparative Example 3 using a forming jig that does not use a positioning pin, a positional shift occurs between the upper surface jigs, and the resin on the inner side surface of the spacer that is shifted inward from the light-shielding film is hardened during photocuring to generate cracks. It was observed.

  In the Example of this invention, it was excellent in workability | operativity compared with the comparative example, and the obtained molded article external appearance was also favorable.

  According to the present invention, it is possible to suppress problems caused by shrinkage due to curing shrinkage of the photocurable resin, as compared with the prior art in which a photocurable resin cured product is molded using a transparent mold, and Since the production cost of the mold can be suppressed, it can be suitably used for a small amount of production or trial production.

DESCRIPTION OF SYMBOLS 1 Spacer 2 Upper surface member 3 Lower surface member 4 Connection member 5 Central space 6 Inlet 7 Connection hole 8 Transparent plate 9 Light shielding member 10 Transmission port 11 Connection hole 12 Transparent plate 13 Light shielding member 14 Transmission port 15 Connection hole 16 Light shielding part 17 Light transmission Part 18 Actinic rays

Claims (4)

A spacer having a central space formed in the central portion of the plate-like member, and an inlet that connects the central space and the outer edge of the plate-like member;
An upper surface member disposed on the upper surface of the spacer and covering the upper surface of the central space;
A lower surface member disposed on the lower surface of the spacer and covering the lower surface of the central space;
A molding jig comprising a connecting member for fixing the spacer, the upper surface member, and the lower surface member,
The upper surface member and the lower surface member are composed of a transparent plate that transmits actinic rays and a light-shielding member attached to one surface of the transparent plate,
The light shielding member has a transmission port formed by cutting out the light shielding member at a central portion,
A molding jig, wherein the central space includes a light shielding portion whose upper and lower surfaces are covered with the light shielding member, and a light transmitting portion whose upper and lower surfaces are not covered with the light shielding member.   The forming jig according to claim 1, wherein the light shielding member is a light shielding tape including an adhesive tape on one side. A method for producing a photocurable resin cured product for molding a photocurable resin using the molding jig according to claim 1,
A filling step of injecting a photocurable resin from the injection port and filling the central space with the photocurable resin;
A method for producing a photocurable resin cured product, comprising an irradiation step of irradiating an actinic ray toward the forming jig and transmitting the actinic ray to the translucent part.   The photocurable resin volume fraction reduced by photocuring shrinkage in the irradiation step is uncured in the light shielding portion and / or the uncured photocurable resin in the injection port. The method for producing a photocurable resin cured product according to claim 3, wherein the photocurable resin cured product is replenished.