JP6666947B2 - Thermosetting composition and method for producing the thermosetting resin - Google Patents

Description

  The present invention relates to a thermosetting composition and a method for producing the thermosetting resin.

  2. Description of the Related Art A light emitting device using an optical semiconductor such as a light emitting diode (LED), which has become popular in recent years, usually has a light emitting device on a lead frame of a molded body formed integrally with a lead frame in a concave shape using a synthetic resin as a reflector (reflector). It is manufactured by fixing a semiconductor (LED) and sealing it with a sealing material such as an epoxy resin or a silicone resin.

As a material for a reflective material, Patent Document 1 discloses a cured product in which a thermosetting resin such as an acrylate resin is blended with a white pigment such as titanium oxide to have excellent heat resistance and weather resistance and excellent adhesion to peripheral members. Are disclosed.
When titanium oxide, which is a typical white pigment, is used, the viscosity of the thermosetting composition is easily increased, and the fluidity of the liquid is impaired. If the fluidity of the liquid is poor, when forming the resin molded product on the lead frame, the lead frame molded body is warped or the reflector is not filled, voids or burrs are generated, and there is a problem in mass productivity of the light emitting device. It is also required that even if the thermosetting composition is stored at room temperature, it has little effect on continuous moldability.

WO 2012/056972 pamphlet

An object of the present invention is to provide a thermosetting composition having excellent continuous moldability, which prevents the formation of voids and prevents the occurrence of voids when molding a reflector on a lead frame. .
Another object of the present invention is to form a thermosetting composition having excellent continuous formability, which prevents unfilling and void formation of the obtained molded product when molding a reflector on a lead frame and suppresses the occurrence of burrs. The present invention provides a method and a method for producing a thermosetting resin.

According to the present invention, the following thermosetting composition and the like are provided.
1. It contains the following components (A) to (C),
A thermosetting composition having a shear viscosity at 25 ° C. of 10 s ⁻¹ to 1 Pa · s or more and 500 Pa · s or less, and a shear rate at 25 ° C. of 100 s ⁻¹ to 0.3 Pa · s or more and 100 Pa · s or less.
(A) a (meth) acrylate compound having a viscosity of 1 to 300 mPa · s at 25 ° C. and having an ester-bonded substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms; (B) spherical silica (C) 1.) White pigment The content of the component (B) is 10 to 90% by mass and the content of the component (C) is 1 to 80% by mass with respect to 100% by mass of the total of the components (A) to (C). 3. The thermosetting composition according to item 1.
3. The (meth) acrylate compound is one or more selected from a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isobonyl group, and a substituted or unsubstituted dicyclopentanyl group. 3. The thermosetting composition according to 1 or 2, which is a (meth) acrylate compound in which an alicyclic hydrocarbon group is ester-bonded.
4. The composition further comprises one or more components selected from the following components (D) to (F),
The content of the component (A) is 1 to 80% by mass and the content of the component (B) is 10 to 90% by mass with respect to the total of 100% by mass of the components (A) to (F). 4. The thermosetting composition according to any one of items 1 to 3.
(D) Monofunctional (meth) acrylate compound having (meth) acrylic acid or a polar group (E) Monofunctional (meth) acrylate compound other than the components (A) and (D) (F) Other than the component (A) 4. at least one compound selected from the group consisting of polyfunctional (meth) acrylate compounds; 5. The thermosetting composition according to any one of 1 to 4, wherein the spherical silica is subjected to (meth) acrylsilane surface treatment.
6. The thermosetting composition according to any one of 1 to 5, wherein the spherical silica has a primary particle average particle size of 0.1 to 100 µm.
7. The thermosetting composition according to any one of 1 to 6, further comprising one or more components selected from the following components (G) and (H).
(G) a plate-like filler (H) a step of supplying the thermosetting composition according to any of the nanoparticles 8.1 to 7 into a plunger,
A step of filling the cavity in a mold with the thermosetting composition filled in the plunger, by the plunger.
Thermosetting the thermosetting composition in the cavity, and extruding the thermosetting thermosetting resin,
A method for producing a thermosetting resin comprising:
9. 9. The method for producing a thermosetting resin according to 8, wherein the mold temperature of the cavity is 100 ° C. or more and 180 ° C. or less.
10. In the step of filling the cavity in a mold by the plunger with the thermosetting composition filled in the plunger, the thermosetting composition is passed through a flow path temperature-controlled to 50 ° C. or less. 10. The method for producing a thermosetting resin according to 8 or 9, wherein the resin is filled in a cavity in a mold.
11. In the step of filling the cavity in a mold with the plunger with the thermosetting composition filled in the plunger, the flow of the thermosetting composition into a flow path between the plunger and the cavity is performed. The method for producing a thermosetting resin according to any one of items 8 to 10, further comprising a gate system for interrupting heat transfer.
12. Opening the gate of the gate system, filling the cavity in a mold with the thermosetting composition,
The thermosetting increases the injection pressure of the thermosetting composition after the start of the curing, performs a pressure holding before the completion of the curing, and after the pressure holding is completed, closes the gate of the gate system to complete the thermosetting. A method for producing the thermosetting resin according to the above.
13. The method for producing a thermosetting resin according to any one of 8 to 12, wherein the filling step and the thermosetting step are performed within 0.2 to 3 minutes.

ADVANTAGE OF THE INVENTION According to this invention, when molding a reflector to a lead frame, it can provide the thermosetting composition which is excellent in continuous moldability which prevents unfilling of the obtained molded product and generation | occurrence | production of a void, and suppresses generation | occurrence | production of a burr.
According to the present invention, when molding a reflector on a lead frame, a method for molding a thermosetting composition excellent in continuous moldability that prevents unfilled and voids in the resulting molded article and suppresses occurrence of burrs, A method for producing a thermosetting resin can be provided.

It is a schematic sectional drawing of the filling device which can be used for the manufacturing method of the thermosetting resin of this invention. It is a schematic sectional drawing of the metal mold | die of the molding machine which can be used for the manufacturing method of the thermosetting composition of this invention. It is a figure showing relation between viscosity and time concerning one embodiment of a manufacturing method of a thermosetting resin of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic sectional drawing which shows one Embodiment of the board | substrate for mounting an optical semiconductor element using the thermosetting composition of this invention, and an optical semiconductor light emitting device, (a) is sectional drawing of a lead frame, (b) 1 is a sectional view of an optical semiconductor element mounting substrate, and FIG. 1C is a sectional view of an optical semiconductor light emitting device. It is a schematic sectional drawing which shows another embodiment of the board | substrate for mounting an optical semiconductor element and the optical semiconductor light emitting device using the thermosetting composition of this invention, (a) is sectional drawing of a lead frame, (b) () Is a cross-sectional view of the optical semiconductor element mounting substrate, and (c) is a cross-sectional view of the optical semiconductor light emitting device.

[Thermosetting composition]
The thermosetting composition of the present invention contains the following components (A) to (C), has a shear viscosity of 10 s ⁻¹ at 25 ° C. of ¹ Pa · s to 500 Pa · s, and a viscosity of 100 s ⁻¹ at 25 ° C. The shear rate is 0.3 Pa · s or more and 100 Pa · s or less.
(A) A substituted or unsubstituted (meth) acrylate compound having a viscosity of 1 to 300 mPa · s at 25 ° C. and having an ester-bonded substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms.
(B) Spherical silica (C) White pigment

The thermosetting composition of the present invention (hereinafter, sometimes simply referred to as the composition of the present invention) has a viscosity of the composition containing the above components (A) to (C) at 25 ° C. and a shear viscosity of 10 s ⁻¹ . Is not less than 1 Pa · s and not more than 500 Pa · s, and the shear rate of 100 s ⁻¹ at 25 ° C. is not less than 0.3 Pa · s and not more than 100 Pa · s. Can be suppressed. In addition, excellent room temperature storage properties can be exhibited.
If each shear rate is not satisfied and the shear rate is low, a large amount of burrs will be generated, and there is a possibility that deburring work may occur on the molding surface, resulting in a poor appearance on the product, which is not desirable. On the other hand, if it is high, the molded article is not filled, and the appearance of the product may be poor, which is not desirable.
The shear rate of 100 s ^{-1 and} the shear rate of 10 s ^-1 correspond to the first half and the second half, respectively, of injecting a material into the cavity. In this case, the viscosity is unfilled in each state, so that the viscosity at both shear rates is within the above range.To adjust the viscosity of the composition to the above range, the amount of each component included in the composition is appropriately adjusted. Becomes possible. Further, the shear viscosity of the composition can be confirmed by a viscoelasticity measuring device.

Hereinafter, each component contained in the composition of the present invention will be described:
[Component (A): a (meth) acrylate compound having a substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms and having an ester bond having a viscosity of 1 to 300 mPa · s at 25 ° C]
The composition of the present invention has, as the component (A), a substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms having a viscosity at 25 ° C. of 1 to 300 mPa · s, which is ester-bonded (meth). An acrylate compound (hereinafter sometimes referred to as compound (A)).
Since the compound (A) gives a polymer having a high glass transition point, when the composition is used as a material for a reflector for an optical semiconductor, heat resistance and light resistance are improved by including the compound in the composition. Can be done.

The carbon number of the alicyclic hydrocarbon group of the compound (A) is 6 or more, preferably 6 to 30, and more preferably 7 to 15.
The alicyclic hydrocarbon group substituent having 6 or more carbon atoms may have a substituent, and as a substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms, for example, a substituted or unsubstituted adamantyl Groups, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isobonyl group, a substituted or unsubstituted dicyclopentanyl group, and a substituted or unsubstituted cyclohexyl group.
The compound (A) is preferably a (meth) acrylate compound (I) having an adamantyl group represented by the following general formula, a (meth) acrylate compound (II) having an isobornyl group, or a (meth) acrylate compound having a norvol group (III) or a (meth) acrylate compound (IV) having a dicyclopentanyl group.
(In the formulas (I), (II), (III) and (IV), R ¹ each independently represents a hydrogen atom or a methyl group.
X each independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms.
Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
Examples of the oxyalkylene group having 1 to 4 carbon atoms include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these Xs, a single bond is preferable from the viewpoint of heat resistance.
U represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, or ＯO formed by combining two U atoms. k represents an integer of 1 to 15. l shows the integer of 1-8. m shows the integer of 1-11. n shows the integer of 1-15.
When there are a plurality of U in the formula, the plurality of U may be the same or different. )

Compound (A) is more preferably adamantyl methacrylate, 1-norbornyl methacrylate, 1-isobornyl methacrylate, or 1-dicyclopentanyl methacrylate, and more preferably 1-adamantyl methacrylate, 1-norbornyl methacrylate. , 1-isobonyl methacrylate. These compounds have a viscosity at 25 ° C. of 1 to 300 mPa · s.
As the substituted or unsubstituted (meth) acrylate compound having an ester-bonded alicyclic hydrocarbon group having 6 or more carbon atoms, one type may be used alone, or two or more types may be used in combination.

The viscosity of the compound (A) is from 1 to 300 mPa · s, preferably from 1 to 200 mPa · s, and more preferably from 1 to 100 mPa · s. By blending the compound (A) having such a low viscosity into the composition, the filling property between the spherical silica and the white pigment can be increased.
The viscosity of the compound (A) can be measured by, for example, a rheometer or a rotary viscometer.

[Component (B): spherical silica]
Component (B) contains spherical silica (SiO ₂ ).
The amount of the (C) white pigment such as barium titanate which will be described later precipitates easily in the liquid and can be used in a limited amount. However, by using spherical silica in combination, the content of the inorganic substance in the composition should be increased. And the material strength, reflectance, heat resistance, and light resistance can be further improved.
In addition, the fluidity of the composition can be maintained, and the filling property during molding can be increased.

  The primary particle average particle diameter of the spherical silica is, for example, 0.1 to 100 μm, preferably 0.5 to 70 μm, and more preferably 1 to 50 μm, as measured by laser diffraction. Thereby, the filling property of the spherical silica can be enhanced, and the blockage of the molding channel can be suppressed.

The spherical silica is preferably subjected to a surface treatment (particularly, an acrylic silane treatment).
The wettability of the spherical silica can be improved by reacting a hydroxyl group on the surface of the spherical silica with a silane coupling agent (particularly, an acrylic silane coupling agent) to thereby improve the wettability of the spherical silica. ) And the optional components (D), (E) and (F)) can improve the dispersibility of the spherical silica and the strength of the cured product.

The content of the spherical silica in the composition is based on 100% by mass in total of the components (A), (B) and (C), or the optional components (D), (E), (F) and When one or more of (G) and (H) is present, the amount is, for example, 10 to 90% by mass, and preferably 20 to 85% by mass, based on 100% by mass of the total of (A) to (H). , 30 to 80% by mass, more preferably 35 to 80% by mass.
When the content of the spherical silica in the composition is less than 10% by mass with respect to the total mass%, the viscosity becomes low, burrs and room temperature storage property are impaired, and material strength may not be secured as physical properties, If it is more than 90% by mass, the viscosity becomes high and the fluidity may be impaired.

[Component (C): white pigment]
The composition of the present invention contains a white pigment as the component (C).
Specific examples of the white pigment include barium titanate, zirconium oxide, zinc oxide, boron nitride, titanium dioxide, alumina, zinc sulfide, magnesium oxide, potassium titanate, barium sulfate, calcium carbonate, and silicone particles. Among these, barium titanate, zirconium oxide, zinc oxide, boron nitride and titanium dioxide are preferred from the viewpoint of high reflectance and availability, and titanium dioxide is preferred from the viewpoint of higher reflectance. The white pigments can be used alone or in combination of two or more.
In addition, rutile type and anatase type exist in the crystal form of titanium dioxide, and since the anatase type has a photocatalytic function and may deteriorate the resin, the rutile type is preferable in the present invention.

  From the viewpoint of the dispersibility of the white pigment in the composition, the volume average particle diameter of the white pigment is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm, and 0.1 to 1 μm. Is more preferable. The volume average particle size can be determined as D50 in the particle size distribution measurement by a laser light diffraction method.

  The white pigment may be a hollow particle. When the white pigment is a hollow particle, visible light that has passed through the outer shell of the hollow particle is reflected at the hollow part. It is preferable that the difference in the refractive index from the gas to be treated is large. The expectation that exists inside the hollow particles is usually air, but may be an inert gas such as nitrogen or argon, or may be vacuum.

  The white pigment may be appropriately surface-treated with a silicon compound, an aluminum compound, an organic substance, or the like. Examples of the surface treatment include (meth) acrylsilane treatment, alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

The content of the white pigment in the composition is based on a total of 100% by mass of the components (A), (B) and (C), or the optional components (D), (E), (F) and When one or more of (G) and (H) is present, the amount is, for example, 3 to 50% by mass, and preferably 4 to 40% by mass, based on 100% by mass of the total of (A) to (H). , And more preferably 5 to 35% by weight, and even more preferably 5 to 25% by weight.
If the content of titanium oxide in the composition is less than 3% by mass with respect to the total mass%, the whiteness may be impaired, and if it is more than 50% by mass, the viscosity becomes high and the fluidity is impaired. There is a risk.

The composition of the present invention may contain, as an optional component, a polymerizable acrylate compound other than the compound (A). Examples of the optional component include one or more components selected from the following components (D), (E), and (F).
Component (D): (meth) acrylic acid or monofunctional (meth) acrylate compound having a polar group Component (E): monofunctional (meth) acrylate compound other than components (A) and (D) Component (F): Polyfunctional (meth) acrylate compound other than component (A) Hereinafter, component (D) may be referred to as compound (D), component (E) as compound (E), and component (F) as compound (F).

The total content of the compounds (A), (D), (E) and (F) in the composition of the present invention is 100% by mass of the total of the components (A) to (F), or the components (A) to When the total of (G) is 100% by mass, it is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass.
The content of compound (A) in the composition of the present invention is determined by the sum of compounds (A), (D), (E) and (F) when components (D), (E) and (F) are present. Is 100% by mass, preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass.

[Component (D): (meth) acrylic acid or monofunctional (meth) acrylate compound having a polar group]
The compound (D) is (meth) acrylic acid or a monofunctional (meth) acrylate compound having a polar group. It is not a bond of an alicyclic hydrocarbon group having 6 or more carbon atoms, and does not overlap with the compound (A).
Since the compound (D) has polarity, it is included in the composition to form a hydrogen bond or the like with a polar metal surface or the like, thereby improving the adhesion, and the presence of the polar group increases the wettability. improves. The alkylene glycol group may be involved in imparting adhesion, but the alkylene glycol (meth) acrylate is not included in the compound (D).

  Examples of the monofunctional (meth) acrylate compound having a polar group include a (meth) acrylate compound in which a substituent containing an atom other than carbon and hydrogen is ester-bonded. Examples of the substituent include a hydroxyl group and an epoxy group. Glycidyl ether group, tetrahydrofurfuryl group, isocyanate group, carboxyl group, alkoxysilyl group, phosphate group, lactone group, oxetane group, tetrahydropyranyl group, amino group and the like.

  Specific examples of the monofunctional (meth) acrylate compound having a polar group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). ) Acrylate (for example, trade name: 4-HBA, manufactured by Nippon Kasei Co., Ltd.), cyclohexane dimethanol mono (meth) acrylate (for example, trade name: CHMMA, manufactured by Nippon Kasei Co., Ltd.), glycidyl (meth) acrylate, 4-hydroxybutyl Acrylate glycidyl ether (for example, trade name: 4-HBAGE, manufactured by Nippon Kasei Co., Ltd.), tetrahydrofurfuryl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2 -(Meth) acryloyloxy Tyl hexahydrophthalic acid, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyl Methyldiethoxysilane, 2- (meth) acryloyloxyethyl phosphate, bis (2- (meth) acryloyloxyethyl) phosphate, KAYAMER PM-2, KAYAMER PM-21 (trade name, manufactured by Nippon Kayaku), γ-butyl lactone (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl), (meth) acrylic acid (3-ethyl-3-oxetanyl), tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylamido Ethyl (meth) acrylate.

  In the present invention, as the compound (D), one kind selected from the above-mentioned (meth) acrylic acid and the above-mentioned (meth) acrylate compound having a polar group may be used alone, or two or more kinds may be used. May be used in combination.

  The content of the compound (D) in the composition of the present invention is preferably from 1 to 40 assuming that the total of the compounds (A), (D), (E) and (F) is 100% by mass from the viewpoint of adhesion. %, More preferably 5 to 15% by mass, and even more preferably 7 to 25% by mass.

[Component (E): Monofunctional (meth) acrylate compound other than components (A) and (D)]
[Component (F): polyfunctional (meth) acrylate compound other than component (A)]
Compound (E) is a monofunctional (meth) acrylate compound other than compounds (A) and (D). By containing the compound (E) in the composition of the present invention, the viscosity and the hardness of the cured product can be adjusted, and the occurrence of cracks and the like can be suppressed.
Compound (F) is a polyfunctional (meth) acrylate compound other than compound (A). Polyfunctional (meth) acrylate compounds other than the compounds (A), (D) and (E) may be contained in the composition within the range not impairing the effects of the present invention from the viewpoint of mechanical strength and curing speed. Good.

  Examples of the (meth) acrylate compounds (compounds (E) and (F)) other than the compounds (A) and (D) include, for example, (meth) acrylate-modified silicone oil, (meth) acrylate having an aliphatic hydrocarbon group, Examples include at least one (meth) acrylate compound selected from the group consisting of polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more, urethane acrylate, epoxy acrylate, and polyester acrylate. As the compound (E), a monofunctional (meth) acrylate compound can be selected from these and used. Further, as the compound (F), a polyfunctional (meth) acrylate compound can be selected from these and used.

  The (meth) acrylate-modified silicone oil that can be used in the present invention is a compound having an acryl group and / or a methacryl group at a terminal and preferably containing a dialkylpolysiloxane in a skeleton. This (meth) acrylate-modified silicone oil is a modified product of dimethylpolysiloxane in many cases, but all of the alkyl groups in the dialkylpolysiloxane skeleton are replaced by an alkyl group other than a phenyl group or a methyl group instead of a methyl group, or Some may be substituted. Examples of the alkyl group other than the methyl group include an ethyl group and a propyl group. Commercially available products of such compounds include single-end reactive silicone oils (eg, X-22-174DX, X-22-2426, X-22-2475) and double-ended reactive silicone oils (eg, X-22-164A). , X-22-164C, X-22-164E) (all manufactured by Shin-Etsu Chemical Co., Ltd., all trade names), methacrylate-modified silicone oils (for example, BY16-152D, BY16-152, BY16-152C) (all manufactured by Toray) -Dow Corning Co., Ltd. (both are trade names) can be used.

  Further, as the (meth) acrylate-modified silicone oil, a polydialkylsiloxane having an acryloxyalkyl terminal or a methacryloxyalkyl terminal can also be used. Specifically, an ABA-type triblock consisting of methacryloxypropyl-terminated polydimethylsiloxane, (3-acryloxy-2-hydroxypropyl) -terminated polydimethylsiloxane, acryloxy-terminated ethylene oxide dimethylsiloxane (A block) and ethylene oxide (B block) is used. Polymers, methacryloxypropyl-terminated branched polydimethylsiloxanes and the like can be mentioned.

The (meth) acrylate having an aliphatic hydrocarbon group that can be used in the present invention is a compound in which a (meth) acrylate group is bonded to a residue obtained by removing a hydrogen atom from an aliphatic hydrocarbon compound.
Alkanes are preferred as the aliphatic hydrocarbon compound which can be used in the present invention to induce the (meth) acrylate having an aliphatic hydrocarbon group, and from the viewpoint of the physical properties of the cured product of the present invention, the alkane has 12 or more carbon atoms. Alkanes are more preferred.

  In the (meth) acrylate having an aliphatic hydrocarbon group that can be used in the present invention, the number of (meth) acrylate groups is not particularly limited, and may be one or more. When the number of (meth) acrylate groups is one, the aliphatic hydrocarbon group is preferably an alkyl group, more preferably 12 or more carbon atoms (preferably 12 to 24 carbon atoms, more preferably 12 to 18 carbon atoms). ) Is a linear alkyl group. When the number of (meth) acrylate groups is two, the aliphatic hydrocarbon group is preferably an alkylene group, more preferably 12 or more carbon atoms (preferably 12 to 24 carbon atoms, more preferably 12 to 18 carbon atoms). ) Is a linear alkylene group.

  Specific examples of the alkyl group having 12 or more carbon atoms include dodecyl group (including lauryl group), tridecyl group, tetradecyl group, hexadecyl group, octadecyl group (including stearyl group), eicosyl group, tricontyl group, and tetracontyl group. No. The alkyl group and alkylene group having 12 or more carbon atoms may be an alkyl group and an alkylene group derived from a hydride of a polymer such as polybutadiene and polyisoprene. Specific examples of the alkylene group having 12 or more carbon atoms include a divalent residue obtained by removing a hydrogen atom from the above alkyl group.

  Specific examples of the (meth) acrylate having an aliphatic hydrocarbon group include lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, and eicosyl (meth) acrylate. Acrylates having a hydrogenated polybutadiene or hydrogenated polyisoprene skeleton such as acrylate, triacontyl (meth) acrylate, tetracontyl (meth) acrylate, or hydrogenated polybutadiene di (meth) acrylate, hydrogenated polyisoprene (meth) acrylate, or Methacryl compounds are exemplified.

By using a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more, the composition of the present invention can provide a cured product having excellent toughness. In the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more that can be used in the present invention, the number of (meth) acrylate groups is not particularly limited, and may be one or more.
The number average molecular weight of the compound is preferably from 400 to 10,000, more preferably from 450 to 5,000, from the viewpoint of toughness and adhesion, and the compatibility with components (A) and (D). Preferably it is 500-3,000.

  Specific examples of the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and ethoxylated trimethylolpropanetriene. (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and the like. Of these, polyethylene glycol di (meth) acrylate is preferred from the viewpoint of toughness and adhesion.

  The urethane acrylate, epoxy acrylate, and polyester acrylate that can be used in the present invention preferably do not contain an aromatic group from the viewpoint of light resistance. The number average molecular weight of the compound is determined by the toughness and the difference between components (A) and (D). From the viewpoint of compatibility, it is preferably 100 to 100,000, more preferably 500 to 80,000, and still more preferably 1,000 to 50,000.

  Other specific examples of the monofunctional or polyfunctional (meth) acrylate compounds (compounds (E) and (F)) that can be used in the present invention include di (meth) acrylate, which is polyethylene glycol having a number average molecular weight of less than 400. Polypropylene glycol di (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isooctyl (meth) acrylate, isodecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethylhexyldiglycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl Recohol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol dimethacrylate 2-methyl-1,8-octanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol acrylic acid hydroxypivalate adduct, 2-hydroxy- 3-acryloyl oki Cypropyl (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated glycerin (meth) acrylate, propoxylated glycerin (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, .epsilon.-caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate.

In the present invention, as the compound (E), one of the above monofunctional (meth) acrylate compounds can be used alone, or two or more can be used in combination.
The content of the compound (E) in the composition of the present invention is preferably 10% by mass with the total of the compounds (A), (D), (E) and (F) being 100% by mass from the viewpoint of toughness and adhesion. To 80% by mass, more preferably 15 to 60% by mass, and still more preferably 15 to 50% by mass.

In the present invention, as the compound (F), one of the polyfunctional (meth) acrylate compounds other than the component (A) can be used alone or in combination of two or more.
The content of the compound (F) in the composition of the present invention is preferably from the viewpoint of not impairing the effects of the present invention, assuming that the total of the compounds (A), (D), (E) and (F) is 100% by mass. Is 5 to 60% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass.

The composition of the present invention preferably further comprises one or more components selected from the following components (G) and (H):
(G) Plate-like filler (H) Nanoparticle

[Component (G): plate-like filler]
By containing the plate-like filler as the component (G), the viscosity of the composition and the hardness of the obtained cured product can be adjusted, and burrs at the time of molding the composition can be suppressed.
Examples of the plate-like filler include talc, kaolin, mica, clay, sericite, glass flake, synthetic hydrotalcite, various metal foils, graphite, molybdenum disulfide, tungsten disulfide, boron nitride, plate-like iron oxide, and plate-like carbonate. Calcium, plate-like aluminum hydroxide and the like. Among them, talc, kaolin, mica, clay, graphite, and glass flake are preferable, and talc is more preferable in that no decrease in reflectance is observed by blending.
In addition, a plate-like filler can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (G) in the composition is, for example, 1 to 30% by mass, and preferably 3 to 20% by mass with respect to the total 100% by mass of (A) to (H). More preferably, it is 5 to 15% by mass.

By containing the nanoparticles as the component (H), the viscosity of the composition can be adjusted, the storage stability of the composition at room temperature can be maintained, and problems during molding can be reduced.
As nanoparticles, silver, gold, silicon, silicon carbide, silica, aluminum oxide, copper oxide, iron oxide, cobalt oxide, titanium oxide, titanium carbide, zinc oxide, zirconium oxide, cerium oxide, ITO, ATO, hydroxyapatite, Graphene / graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, fullerene, diamond, mesoporous carbon, and the like. Preferably, silicon carbide, silica, aluminum oxide, titanium oxide, titanium carbide, zinc oxide, zirconium oxide is preferable, and silica, aluminum oxide, titanium oxide, titanium carbide, zinc oxide, zirconium oxide is preferable in that whiteness can be maintained. More preferred.
The nanoparticles can be used alone or in combination of two or more.

  The content of the component (H) in the composition is, for example, 0.05 to 10% by mass and 0.07 to 7% by mass based on 100% by mass in total of (A) to (H). And more preferably 0.1 to 5% by mass. When the content is 0.05% by mass or less, stability during storage at normal temperature is poor, and sedimentation of solid components may occur. When the content is 10% by mass or more, deterioration in appearance (transferability) of a molded product is deteriorated. Can occur.

The components (A), (D), (E) and (F) of the thermosetting composition of the present invention reduce the viscosity of the thermosetting composition, and the components (B), (C), (G) and (H) increases the viscosity of the curable composition.
25 ° C. The shear viscosity of ^{10s -1} 1 Pa · s or more 500 Pa · s or less at the thermosetting composition, from the viewpoint of the shear rate of 100s ^-1 and less 0.3 Pa · s or more 100 Pa · s at 25 ° C., The content of the components (A), (D), (E) and (F) in the thermosetting composition is 7 to 50% by mass with respect to 100% by mass in total of (A) to (H). Yes, it is preferably 7 to 35% by mass, more preferably 8 to 25% by mass, and the content of the components (B), (C), (G) and (H) in the thermosetting composition is as follows: 50 to 93% by mass, more preferably 60 to 93% by mass, even more preferably 75 to 92% by mass, based on 100% by mass of the total of (A) to (H).
By adjusting the viscosity of the thermosetting composition to the above-mentioned viscosity range, continuous moldability is excellent, and occurrence of burrs in the obtained molded product can be suppressed.

The thermosetting composition of the present invention may contain the components (A), (B) and (C), and optionally the components (D), (E), (F), (G) and (H). May be included.
In the thermosetting composition of the present invention, the total content of the components (A) to (H) may be, for example, 85% by weight or more, 95% by weight or more, or 99% by weight or more, and the component (A) To (H) alone.

[Additive]
The thermosetting composition of the present invention comprises, in addition to the components (A) to (H), additives such as a polymerization initiator, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, an inorganic filler, and a coloring agent. Agents, antistatic agents, lubricants, release agents, flame retardants, leveling agents, defoamers, and the like can be included in a range that does not impair the effects of the present invention. Known additives can be used as these additives.
Hereinafter, suitable additives for the composition of the present invention will be described.

(Polymerization initiator)
A cured product can be obtained by polymerizing the composition of the present invention with heat. To promote the polymerization reaction, the composition may contain a polymerization initiator. The polymerization initiator is not particularly limited, and examples include a radical polymerization initiator.
Although it does not specifically limit as a radical polymerization initiator, For example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, alkyl peresters (peroxyesters), And peroxycarbonates.

  Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and the like.

  Specific examples of hydroperoxides include 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide and the like. Is mentioned.

  Specific examples of diacyl peroxides include diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, dilauroyl peroxide, dibenzoyl peroxide, m-toluylbenzoyl peroxide, succinic peroxide, and the like. Is mentioned.

  Specific examples of dialkyl peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t- Butyl cumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3 and the like.

  Specific examples of peroxyketals include 1,1-di-t-hexylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-hexylperoxycyclohexane, 1,1-di-t- Butylperoxy-2-methylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, butyl 4,4-bis-t-butylperoxypentanoate and the like.

  Specific examples of alkyl peresters (peroxyesters) include 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, and t-butylperoxyneodecanoate. Ethate, t-hexylperoxyneohdecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,1 3,3-tetramethylbutylperoxy-3,5,5-tri Tyl hexanate, t-amyl peroxy 3,5,5-trimethyl hexanoate, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy benzoate, dibutyl peroxy trimethyl Adipate, 2,5-dimethyl-2,5-di-2-ethylhexanoylperoxyhexane, t-hexylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxylaurate, t -Butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di-benzoylperoxyhexane, and the like.

  Specific examples of peroxycarbonates include di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, di-4-tert-butylcyclohexylperoxycarbonate, di-2-ethylhexylperoxycarbonate, di-sec-butylperoxycarbonate, Di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate, 1, 6-bis (t-butylperoxycarboxyloxy) hexane and the like.

In the present invention, the above radical polymerization initiators can be used alone or in combination of two or more.
The content of the radical polymerization initiator in the composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of components (A) to (H). Parts by weight.

(Antioxidant)
Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a vitamin-based antioxidant, a lactone-based antioxidant, and an amine-based antioxidant.

  Examples of phenolic antioxidants include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and β- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionic acid stearyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di- t-butyl-4-hydroxybenzyl) isocyanurate, tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2,6-di-t-butyl-4-methyl Phenol, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate and the like, for example, IRGANOX 1010, IRGANOX 1076, IRGANOX 1330, IRGANOX 3114, IRGANOX 3125, IRGANOX 3790 (manufactured by BASF), CYANOX 1790 (manufactured by Cyanamid), SUMILIZER BHT, SUMILIZER GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) Goods can be used (all are trade names).

  Examples of the phosphorus antioxidant include tris (2,4-di-t-butylphenyl) phosphite and 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f ] [1,3,2] dioxaphosphepin-6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl] oxy] -ethyl] ethanamine, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phos Phyto, distearylpentaerythritol diphosphite and the like, for example, IRGAFOS 168, IRGAFOS 12, IRGAFOS 38 (all manufactured by BASF), ADK STAB 329K, Use commercially available products such as ADK STAB PEP36, ADK STAB PEP-8 (all manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston 618, Weston 619G, Weston 624 (all manufactured by GE). (Both are trade names).

  Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), pentane Erythritol tetrakis (3-laurylthiopropionate) and the like, for example, DSTP "Yoshitomi", DLTP "Yoshitomi", DLTOIB, DMTP "Yoshitomi" (all manufactured by API Corporation), Seenox 412S (Cipro) Commercial products such as Kasei Co., Ltd., Cyanox 1212 (Cyanamide Co., Ltd.), and SUMILIZER TP-D (Sumitomo Chemical Co., Ltd.) can be used (all are trade names).

Examples of vitamin-based antioxidants include tocopherol, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) coumarone-6-ol, and, for example, IRGANOX E201 Commercial products such as (manufactured by BASF) can be used.
As the lactone-based antioxidant, those described in JP-A-7-233160 and JP-A-7-247278 can be used. In addition, HP-136 (trade name, manufactured by BASF, compound name: 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one) or the like may be used. Can also.

  Examples of the amine-based antioxidant include commercially available products such as IRGASTAB FS 042 (manufactured by BASF) and GENOX EP (manufactured by Crompton, compound name: dialkyl-N-methylamine oxide) (all are trade names). .

  These antioxidants can be used alone or in combination of two or more. The content of the antioxidant in the composition of the present invention is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the total of components (A) to (H) from the viewpoint of not impairing the effects of the present invention. , More preferably 0.02 to 2 parts by mass.

(Light stabilizer)
As the light stabilizer, any one such as an ultraviolet absorber and a hindered amine light stabilizer can be used, but a hindered amine light stabilizer is preferable.
Specific examples of the hindered amine light stabilizer include ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA. -94 (all made by ADEKA), Tinuvin 123, 144, 440, 662, 765, 770DF, Tinuvin XT 850 FF, Tinuvin XT 855 FF, Chimassorb 2020, 119, 944 (all made by BASF), Hostavin N30H Co., Ltd.), Cyasorb UV-3346, UV-3526 (Cytec), Uval 299 (GLC), Sanduvor PR-31 (Clariant) and the like (all are trade names).

  Specific examples of the ultraviolet absorbent include ADK STAB LA-31, ADK STAB LA-32, ADK STAB LA-36, ADK STAB LA-29, ADK STAB LA-46, ADK STAB LA-F70, ADK STAB 1413 (manufactured by ADEKA), Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 213, Tinuvin 571, Tinuvin 765, Tinuvin 1577ED, Chimassorb 81, Tinuvin 120 (and others, BASF). Above all, the Tinuvin series manufactured by BASF is preferred, and Tinuvin 765 is more preferred.

  These light stabilizers can be used alone or in combination of two or more. The content of the light stabilizer in the composition of the present invention is preferably 0.005 to 5 parts by mass based on 100 parts by mass of the total of components (A) to (H) from the viewpoint of not impairing the effects of the present invention. , More preferably 0.02 to 2 parts by mass.

(Release agent)
The internal release agent dissolves and disperses well in the (meth) acrylate compound. Furthermore, when it is cured, it is in a low-viscosity molten state, making it easy for molecular movement, and is separated from the resin component that cures during curing. It is required that, by being present between the mold and the hardening component, it has releasability, and that at the time of demolding, a low viscosity in a molten state can further enhance the releasability. Can be Although there is no particular designation as the internal release agent, an aliphatic compound is desirable.

  The aliphatic compound used as the internal release agent preferably has a melting point in the range of −40 ° C. to 180 ° C., and more preferably in the range of −30 ° C. to 180 ° C. By setting the melting point of the aliphatic compound to -40 ° C. or higher, good releasability can be exhibited without vaporization during curing and generation of bubbles or the like in the product to cause poor appearance. Further, by setting the melting point of the aliphatic compound to 180 ° C. or lower, solubility is improved, and good appearance and releasability are obtained.

As the aliphatic compound, a compound represented by the following formula (V) is preferable.
(In the formula (V), R ⁴ represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms.
W represents a hydrogen atom, a metal atom or a hydrocarbon group having 1 to 8 carbon atoms.
When W is a metal atom, O and W are ionically bonded. )

The aliphatic hydrocarbon group of R ^{4 in} the formula (V) may have a linear structure or a branched structure, and the bonding state in the molecular chain may include only a single bond or may include a multiple bond. Specifically, it is an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. The number of multiple bonds in the aliphatic unsaturated hydrocarbon group may be one or more.

The hydrocarbon group of R ⁴ has 6 to 30 carbon atoms. If the number of carbon atoms is less than 6, it will volatilize during curing, etc., so that the aliphatic compound cannot be present between the mold and the material, so that the releasability will not be developed or bubbles will remain in the material. there is a possibility. When the number of carbon atoms is more than 30, the mobility of the material becomes low, and the material becomes opaque due to the incorporation of an aliphatic compound into the material, or the material does not exhibit releasability. The hydrocarbon group of R4 preferably has 6 to 26 carbon atoms, and more preferably 8 to 22 carbon atoms.

Examples of the metal atom in W in the formula (V) include alkali metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, zinc, and aluminum.
When W is an alkaline earth metal or aluminum, it is divalent or higher, so the formula (V) of the aliphatic compound is represented by (R ⁴ —CO—O) _q —W, where q is 2 to 4. Become.

The aliphatic hydrocarbon group for W in the formula (V) may have a linear structure or a branched structure, and the bonding state in the molecular chain may include only a single bond or may include a multiple bond. Specifically, it is an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group.
The number of multiple bonds in the aliphatic unsaturated hydrocarbon group may be one or more. The aliphatic hydrocarbon group represented by W has 1 to 8 carbon atoms. When the number of carbon atoms is 8 or more, an increase in the melting point and a decrease in solubility of the aliphatic compound are caused, and the aliphatic compound is taken into the resin component at the time of curing or is unevenly distributed. Or become opaque. The preferred carbon number of the aliphatic hydrocarbon group for W is 1-6.

In order to exhibit good releasability, when W of the aliphatic compound represented by the general formula (V) is a hydrogen atom, R ⁴ is an aliphatic hydrocarbon group having 6 to 20 carbon atoms. Preferably, there is. When W is a metal atom, R ⁴ is preferably an aliphatic hydrocarbon group having 6 to 18 carbon atoms. When W is an aliphatic hydrocarbon group, the total number of carbon atoms of the aliphatic hydrocarbon group of R ⁴ and W is preferably 7 to 30.

  The content of the release agent in the present invention is 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the components (A) to (H) in total. If the content of the release agent exceeds 10 parts by mass, the transferability of the mold shape and the shape stability to heat may not be maintained. On the other hand, if the amount is less than 0.01 part by mass, the releasability may not be obtained.

  The composition of the present invention can be prepared by mixing the above components (A) to (H) at a predetermined quantitative ratio. The mixing method is not particularly limited, and any known means such as a stirrer (mixer) can be used. In addition, mixing can be performed at ordinary temperature, under cooling, or under heating, at ordinary pressure, under reduced pressure, or under increased pressure.

The composition of the present invention is a material suitable as, for example, a reflector (reflector) for an optical semiconductor, and can reduce warping and unfilling of a lead frame molded body that may occur during the manufacture of a light emitting device. Further, the mass productivity and the life of the light reflectance of the light emitting device can be improved, and burrs generated after molding can be suppressed. Deburring can be omitted. Thereby, the quality of the molded article after the electrolysis treatment can be improved.
Further, the composition of the present invention is a material that can be used for a long time at the temperature used during molding.

The cured product can be produced by transfer molding, compression molding or injection molding using the composition of the present invention.
In the case of transfer molding, using a transfer molding machine, for example, a mold clamping force of 5 to 20 kN, a molding time of 100 to 190 ° C and a molding time of 30 to 500 seconds, preferably a molding temperature of 100 to 180 ° C and a molding time of 30 to 180 seconds. Can be molded. In the case of compression molding, it can be molded using a compression molding machine at a molding temperature of 100 to 190 ° C. for a molding time of 30 to 600 seconds, preferably at a molding temperature of 110 to 170 ° C. for a molding time of 30 to 300 seconds. In any of the molding methods, post-curing may be performed at, for example, 150 to 185 ° C. for 0.5 to 24 hours.
Using liquid injection molding, for example, molding is performed at a mold clamping force of 10 kN to 40 kN, a molding temperature of 100 to 190 ° C. and a molding time of 30 to 500 seconds, preferably at a molding temperature of 100 to 180 ° C. and a molding time of 20 to 180 seconds. be able to.
When the composition of the present invention is molded by transfer molding, compression molding, liquid resin injection molding, insert molding, or the like, preliminary polymerization may be performed.

[Production method of thermosetting resin]
The method for producing a thermosetting resin of the present invention includes the following steps (1) to (4):
(1) Step of supplying the thermosetting composition of the present invention into a plunger (2) Step of filling the cavity in the mold with the plunger with the thermosetting composition filled in the plunger (3) ) Step of thermosetting the thermosetting composition in the cavity (4) Step of taking out the thermosetting thermosetting resin

Since the thermosetting composition of the present invention is a low-viscosity material, the liquid component in the composition can be filled even if the gap is 1 μm by filling the mold with pressure. On the other hand, since the thermosetting composition of the present invention contains spherical silica and a white pigment, only the resin component of the thermosetting composition is filled in the step of filling the cavity in the mold with the thermosetting composition. The "liquid leakage" phenomenon may occur. Further, since the composition of the present invention is thermosetting, it must not be heated until immediately before molding, and must be sufficiently heated during molding, and may not be completely cured when oxygen is present during heat curing. There is.
In the molding method of the present invention, the use of a plunger-type injection molding machine having a plunger instead of a screw-type injection molding machine allows the occurrence of leakage (back-back flow) and liquid leakage even with a low-viscosity composition. Can be prevented. In addition, since thermosetting is performed in the cavity, thermosetting in the absence of oxygen is possible. Therefore, the molding method of the present invention is preferable as the molding method of the thermosetting resin of the present invention.

FIG. 1 is a diagram showing an embodiment of a molding machine capable of performing the injection molding method of the present invention.
The molding machine of FIG. 1 is an injection molding machine having a plunger mechanism for extruding the thermosetting composition of the present invention into a mold, and includes a filling device 10 having a plunger 11 shown in FIG. ), A decompression device as a deaeration means connected to a pore for deaeration of the cavity 21 in the die 20, although not shown, and a mold. A heating device as a heating means connected to the mold 20 and a cooling device are provided. The molding material is the thermosetting resin of the present invention.

  As the filling device 10, a filling device having a known plunger can be used. Normally, the filling device 10 having the plunger 11 is provided with a feed portion and a non-return prevention function as shown in FIG. 1, and by rotating the screw 12, feeds and agitates the material input from an input port (not shown). In the present embodiment, stirring and mixing are not required because the raw material composition that is a uniform liquid is charged. Therefore, the screw shape is not necessary, and only the material feed by pressure feeding from the inlet and the check prevention function may be used.

  In the method for molding a thermosetting composition according to the present invention, in the step of filling the thermosetting composition supplied into the plunger into the cavity in the mold by the plunger, the flow controlled at a temperature of 50 ° C. or less is used. The cavity is filled in the mold with the thermosetting composition via a passage. When the molding method of the present invention is performed using the apparatus shown in FIG. 2, the flow path corresponds to the flow path 13 of the raw material composition in the filling device 10 and the introduction path in the mold 20, and the cooling unit 14 is used. Thus, the temperature of the flow path may be controlled to 50 ° C. or less.

In the method for molding a thermosetting composition according to the present invention, preferably, in the step of filling the cavity in the mold with the plunger, the flow between the plunger and the cavity is performed. A gate system is provided in the path to block the flow of the curing liquid and the transfer of heat. Hereinafter, the molding method of the present invention will be described with reference to FIG.
When the molding method of the present invention is performed using the apparatus shown in FIG. 2, the needle 223 and the opening 222 correspond to the gate system. As described above, the needle 223 moves toward the movable mold 23 and closes the opening 222, whereby the introduction path 221 is divided just before the heating section 22A, and the composition introduced into the introduction path 221 is cooled by the cooling section 22B. And can block the flow of the composition and the transfer of heat. As a system capable of blocking the flow of the composition and the transfer of heat, there are a valve gate system, a shut-off nozzle system, and the like.
The heating device is a device that heats the heating unit 22A and the movable mold 23. By such heating, the temperature in the cavity 232 (also referred to as “cavity temperature”) can be set to a predetermined temperature. In the molding method of the present invention, preferably, the mold temperature of the cavity is set to 100 ° C. or more and 180 ° or less.
The cooling device is a device that cools the flow path of the raw material composition. Specifically, the cooling unit 22B of the filling device 10 and the mold 20 may be cooled to 10 ° C. or more and 50 ° C. or less.
In the case of injection molding, the needle 15 in FIG. 1 corresponds to the needle 223 in FIG. 2, the flow path 13 in FIG. 1 corresponds to the introduction path 221 in FIG.

  The method for molding a thermosetting resin using the molding machine includes, for example, a step of supplying a predetermined amount of the thermosetting composition into a plunger (supplying step), and a step of supplying the thermosetting composition filled in the plunger. A step of filling a cavity in a mold with a plunger (filling step), a step of thermally curing a thermosetting composition in the cavity (curing step), and a step of removing a cured product obtained by thermosetting a thermosetting resin. (Release step).

(Supply process)
When molding is performed by transfer molding or compression, it can be measured by inserting an appropriate amount of material into a plunger portion in a mold using a supply device such as a syringe.
When molding is performed by injection molding, the raw material composition is injected into the filling device 10 shown in FIG. 1 from an inlet (not shown). The introduced raw material composition is extruded into the fluidizing section 12, and a predetermined amount is measured by the plunger 11. After the end of the weighing or before the injection, the screw 12 moves forward to function as a check valve when the plunger 11 operates. During this time, since the flow path is cooled by the cooling device, the raw material composition flows smoothly without curing.

(Filling process)
The filling step corresponds to FIG.
When the thermosetting composition is injected into the cavity, a vent that allows air in the cavity to escape or a cavity that is connected to a decompression device such as the decompression tube 240 in FIG. Needs to be decompressed. The reason is that in the process of injecting the thermosetting composition into the cavity and completely filling it, the vent is to release the air in the cavity, and the decompression in the cavity can be completely filled by leaving no air. In order to If this mechanism is not provided, a mechanism that allows air in the cavity to escape when the material is filled is required (for example, a vent mechanism).
To mold the thermosetting composition, first, the movable mold 23 is brought close to the fixed mold 22 and the mold is clamped (FIG. 2A). The movement of the movable mold 23 is temporarily stopped at a position where the elastic member 238 of the movable mold 23 contacts the elastic member 224 of the fixed mold 22.

The filling of the thermosetting composition into the cavity is performed by opening the gate of the gate system (moving the needle 223 to the fixed mold 22 side) and filling the cavity 21 in the mold with the thermosetting composition. . The heating part 22A provided in the movable mold 23 and the fixed mold 22 is always heated, and the cavity temperature is 60 ° C or higher, preferably 90 ° C or higher and 180 ° C or lower, particularly preferably 110 ° C or higher and 170 ° C or lower. Set to be.
When using an injection molding machine, when starting injection from the injection section into the cavity, open the nozzle of the shut-off nozzle (or valve gate in some cases), move the plunger of the injection section, and remove the thermosetting component. Inject into the cavity. When a transfer molding machine is used, since everything from the inside of the plunger to the cavity is cured, it is only necessary that the material can flow into the cavity, and it is not necessary to shut off the transfer of heat.

(Curing process)
FIG. 2C corresponds to the curing step.
When the filling of the raw material composition into the cavity 21 is completed, the curing of the raw material composition is started at the same time. However, in order to improve the transferability of the molded product, it is necessary to apply a predetermined pressure to cure the molded product. . That is, it is preferable that the plunger 11 is pressurized to 1.0 MPa or more and 15 MPa or less. This pressure applied to the raw material composition in order to improve transferability is referred to as holding pressure.
In the curing step, preferably, the injection pressure of the thermosetting composition is increased after the start of the curing, the holding pressure is performed before the completion of the curing, and after the completion of the holding, the gate of the gate system is closed to perform the thermosetting. Specifically, the way to close the gate is to advance the needle 223 and close the opening 222. In the molding process, the cooling device is operated to cool the entire flow path of the raw material composition, that is, the cooling unit 22B provided in the filling device 10 of the molding machine and the fixed mold 22 of the mold 20. At this time, the entire flow path is preferably maintained at 10 ° C. or higher and 50 ° C. or lower, particularly preferably at 30 ° C. or lower.

  Hereinafter, the pressure holding by the plunger 11 and the timing of starting the pressure holding will be described. FIG. 3 is a diagram showing the relationship between the viscosity of the raw material composition and time in the present embodiment. In FIG. 3, a period P1 from the injection of the material into the cavity to the completion of the filling corresponds to an induction period from when heat is applied to the material and curing starts. The curing process is divided into two stages: an initial stage of curing P2 from when the material starts to be cured by applying heat to a stage of curing, and a late stage of curing P3 in which the curing is completed. The viscosity of the raw material composition remains unchanged at the low viscosity in the induction period P1, shows a significant change in viscosity from a low viscosity to a high viscosity in the initial stage of curing P2, and changes to a high viscosity state in the late stage of curing P3. It rises slowly.

In the initial stage of curing P2, the raw material composition shrinks due to not only a change in viscosity from a liquid to a solid but also a change in volume. Therefore, in actual molding, unless pressure is applied to the raw material composition, the molded article will have poor transferability. In order to improve the transferability, it is necessary to apply pressure (holding pressure) to the raw material composition, bring the raw material composition into close contact with the mold 20, and supplement the raw material composition from the gate portion.
However, in the case of a low-viscosity material such as the raw material composition of the present embodiment, when pressure is applied in a state where the material viscosity is low, because of the low-viscosity material, there is a gap between the fixed mold 22 and the movable mold 23. A failure phenomenon in which the material leaks and hardens (burr), and an operation failure of the extrusion pin due to the penetration of the raw material composition into a gap around the extrusion pin and the like occur. On the other hand, even if pressure is applied in the state where the viscosity is increased in the initial stage of curing P2 or in the state of the final stage of curing P3, the raw material composition has a high viscosity and cannot be deformed by compression, so that transferability cannot be improved. Therefore, in order to obtain a molded article having high transferability, it is necessary to match the timing of starting the pressure holding (the pressure holding start time T) with the timing of shifting from the induction period P1 of the curing process to the initial curing P2.

Here, if the viscosity of the raw material composition in the cavity 21 can be detected, the holding pressure start time T can be determined. However, in order to measure the viscosity of the raw material composition, the raw material composition in the cavity 21 of the mold 20 is required. It is necessary to incorporate a device for measuring the viscosity. This is not practical because the size of the mold 20 is increased, the mechanism is complicated, and the manufacturing cost is significantly increased.
In the present embodiment, the raw material composition starts to contract at the same time as the viscosity increases in the initial stage P2 of curing. Therefore, if the time at which contraction starts is detected, the pressure-holding start time T can be appropriately determined.

In the curing step, by maintaining the pressure under the above-described conditions, sink and distortion of the molded product can be prevented, and transferability can be improved.
After the pressure holding for a certain period of time is completed, the needle 223 is advanced to close the opening 222 as shown in FIG. 2C, and the raw material composition is completely cured by heating for a certain period of time so that an uncured portion does not occur. Let it.
Here advance the plunger 11 by a thermosetting composition was filled into the cavity 21 of the mold 20, the time t ₁ required for filling. When the filling is completed, the plunger 11 stops. When the curing of the raw material composition is started, the thermosetting composition shrinks at the same time, so that the plunger 11 that has been stopped after the completion of the filling step starts to advance again. From the filling process completion, and the time t ₂ required until the plunger 11 starts advancing again by the shrinkage. Furthermore, when the heating time required to completely cure the raw material composition was _{t 3, t 1 + t 2} + t 3 ( total time required for the filling process and the heat curing step) is preferably 0.2 minutes to 3 minutes. More preferably, it is 0.2 to 2 minutes. When the time is 0.2 minutes or less, uncuring may occur, and when the time is 3 minutes or more, it is not preferable from the viewpoint of mass productivity.

(Release process)
FIG. 2D corresponds to the release step.
By separating the movable mold 23 from the fixed mold 22, the cured product in the cavity can be taken out. If the releasability is poor, an ejector mechanism may be appropriately provided in the mold.

[Cured product]
The cured product (thermosetting resin) of the present invention can be obtained by polymerizing and hardening the above-described thermosetting composition of the present invention with heat, and is preferably formed by the production method of the present invention. Things.
The cured product of the present invention can be suitably used, for example, as a reflector for an optical semiconductor light emitting device. The reflective material using the cured product of the present invention does not decrease in reflectance even when used for a long time, has high reflectance in the visible light region, has excellent heat resistance and weather resistance, and has excellent adhesion to peripheral members. .

  The reflective material of the present invention has a high reflectance in the visible light region and a small decrease in the reflectance even when used for a long time. The light reflectance at a wavelength of 450 nm of the reflector of the present invention is preferably 85% or more, more preferably 90% or more, even more preferably 93% or more at an initial value, and after a deterioration test at 150 ° C. for 1,000 hours. Of the light reflectance from the initial reflectance can be preferably at most 20%, more preferably at most 15%, further preferably at most 10%. The light reflectance is determined by the method described in the examples.

[Optical semiconductor light emitting device]
The optical semiconductor light emitting device of the present invention includes the above-described reflector of the present invention. Other configurations of the optical semiconductor light emitting device can be known.
The optical semiconductor element mounting substrate and the optical semiconductor light emitting device of the present invention will be further described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing one embodiment of the optical semiconductor element mounting substrate and the optical semiconductor device of the present invention. FIG. 4A shows a lead frame 510.

  FIG. 4B shows an optical semiconductor element mounting substrate 520 in which a resin molded body is formed as a reflector 521 on the lead frame 510 of FIG. 4A. The optical semiconductor element mounting substrate 520 has a concave portion including a bottom surface including the lead frame 510 and the reflective member 521 and an inner peripheral side surface including the reflective member 521. The resin molded body constituting the reflector 521 is obtained by curing the composition of the present invention.

  FIG. 4C shows a state in which the optical semiconductor element 531 is mounted on the lead frame of the optical semiconductor element mounting substrate of FIG. 4B, and the optical semiconductor element 531 and the other lead frame on which the optical semiconductor element 531 is not mounted. Is bonded by a wire 532, and the concave portion is sealed with a transparent resin (encapsulating resin) 533. A phosphor 534 for converting light emission such as blue light into white light may be included in the sealing resin.

It is a schematic sectional view showing another embodiment of an optical semiconductor element mounting substrate and an optical semiconductor light emitting device of the present invention.
FIG. 5A shows the lead frame 10.
FIG. 5B shows an optical semiconductor element mounting substrate 620 in which a resin molded body is molded as a reflector 621 between the lead frames 610 of FIG. 5A. The optical semiconductor element mounting substrate 620 includes a lead frame 610 and the reflector 621 of the present invention between the lead frames 610.

  FIG. 5C shows an optical semiconductor light emitting device 630 including the optical semiconductor element mounting substrate of FIG. 5B. After the optical semiconductor element 631 is mounted on the lead frame 610 and electrically connected by the bonding wire 632, the sealing resin portion made of the transparent sealing resin 633 is collectively cured and molded by a method such as transfer molding or compression molding. After the optical semiconductor element 631 is sealed, the wafer is diced into individual pieces. A phosphor 634 for converting light emission such as blue light into white light may be included in the sealing resin.

  The size and shape of each part of the optical semiconductor element mounting substrate are not particularly limited and can be set as appropriate. The sealing resin (sealing material) is made of, for example, an epoxy resin, a silicone resin, an acrylate resin, or the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1-30 and Comparative Example 1-10
A thermosetting composition was prepared using the raw materials and composition ratios shown in Tables 1-4, and molded articles were obtained under molding conditions A or B shown below.
In the preparation of the composition, first, the liquid component and the additive component were respectively measured, and these were mixed and stirred. Then, each of the inorganic components was weighed and added, and finally stirred to obtain a composition. The order of blending the inorganic components was (H), (G), (C), and (B).
As the stirrer, a stirrer capable of rotating and revolving was used. The rotation speed was 1000 rpm and the revolution time was 2,000 rpm.

[LTM molding (molding condition A)]
Molding machine: Liquid transfer molding machine G-Line, manufactured by Apic Yamada Co., Ltd.
Flow path and shut-off method: Manual shut-off using a syringe Flow path temperature and cavity temperature in a high-temperature part: measured at 150 ° C. when perbutyl E was used as an additive, and 130 ° C. when perhexa HC was used as an additive. .
Filling time: 10 seconds Filling pressure: 2 MPa (filling time priority)
Holding time: 15 seconds Pressure during holding: 5 MPa
Curing time: 90 seconds

[LIM molding (molding condition B)]
Molding machine: liquid thermosetting resin injection molding machine LA-40S, manufactured by Sodick Co., Ltd.
Flow path and heat shut-off method: use of shut-off nozzle Flow path temperature and cavity temperature of high temperature part: 150 ° C. when perbutyl E was used as an additive, and 130 ° C. when perhexa HC was used as an additive.
Filling time: 10 seconds Filling pressure: 2 MPa (filling time priority)
Holding time: 15 seconds Pressure during holding: 5 MPa
Curing time: 90 seconds

The components used in preparing the thermosetting composition are as follows:
[Component (A): (meth) acrylate compound]
AM: Adamantyl methacrylate (M-104, manufactured by Idemitsu Kosan Co., Ltd., viscosity at 25 ° C .: 10 mPa · s)
IBMA: 1-isobornyl methacrylate (IB-X, manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25 ° C .: 10 mPa · s)

[Components (D), (E), (F): (meth) acrylate compound]
LA: lauryl acrylate (SR335, manufactured by Arkema Corporation)
StMA: Stearyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
SR351: Trimethylolpropane triacrylate (Arkema Corporation)
GMA: glycidyl methacrylate (Blemmer GH, manufactured by NOF Corporation)
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DON-N: 1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
3000 MK: bisphenol A diglycidyl ether methacrylic acid adduct (3000 MK, manufactured by Kyoeisha Chemical Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Hiroshima Wako Co., Ltd.)

[Component (B): spherical silica]
CRS1085-SF630: spherical silica having an average particle size (D50) of 15 μm (manufactured by Tatsumori Co., Ltd.)
CR1015-MSR35TS: spherical silica having an average particle size (D50) of 15 μm (manufactured by Tatsumori Co., Ltd.)
CRS1035-LER4: Tatsumori Co., Ltd. Spherical silica with an average particle size (D50) of 2 μm TS12-046HA: Spherical silica with an average particle size (D50) of 15 μm (manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd. Micron Company)

[Component (C): white pigment]
PC-3: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) Average particle size 0.2 μm

[Component (G): plate-like filler]
TP-A: Talc (Fuji Talc Kogyo Co., Ltd.) Average particle size 5 μm

[Component (H): nanoparticles]
R711: Fumed silica (Nippon Aerosil Co., Ltd.) particle size 5 to 50 nm

[Additive]
Tinuvin 765: UV absorber (manufactured by BASF Japan Ltd.)
StMg: Magnesium stearate (manufactured by NOF Corporation)
StZn: zinc stearate (manufactured by Dainichi Chemical Industry Co., Ltd.)
Partiable E: Organic peroxide (manufactured by NOF Corporation)
Perhexa HC: Organic peroxide (manufactured by NOF Corporation)

The following evaluation was performed about the prepared composition and the obtained molded article. The results are shown in Table 1-4.
(1) Method of Measuring Viscosity The prepared composition was measured for melt viscosity under the following conditions using a viscoelasticity measuring device.
Apparatus name: Physica MCR301 manufactured by Anton Paar
Measurement method: Plate-plate Plate diameter: 25mmφ
Temperature: 25 ° C
Plate, plate interval: 0.6mm
Shear rate: 1 to 200 (1 / s)
The viscosity was defined as the shear viscosity at 10 (1 / s) and 100 (1 / s) in this shear rate region.
In the case where slippage occurs during measurement and measurement is not possible, normal force may be applied in a range where the thickness does not change.

(2) Room temperature storage property When the prepared composition was left at 25 ° C. for 2 days and then molded using the used mold, if short circuit or burr did not occur, “O” was generated, and one of them was generated. Was evaluated as “△”, and both were evaluated as “×”.

(3) Evaluation of Mold and Good Molding The mold for evaluation of moldability is width (10 mm) × length (50 mm) × thickness (1 mm), and width (5 mm) × length (10 mm) × A mold having a vent (thickness: 0.03 mm) was used. In addition, a mold having a width (50 mm) × length (50 mm) × thickness (2 mm) was used as a mold for property evaluation.
(3-1) Evaluation of Formability As a formability evaluation, the occurrence of short circuit was confirmed. In the process of setting the mold to a predetermined temperature and filling between 10 seconds and 15 seconds, voids in the molded product, and if both unfilled occur, ×, one of them is generated Was evaluated as い る when both occurred, and as ○ when neither occurred.
(3-2) Presence or absence of burrs In the process of setting the mold to a predetermined temperature and filling the mold between 10 seconds and 15 seconds, burrs in the molded product visually beyond the end of the vent, and other than the vent Was evaluated as "x" when burr was generated from the part, "△" when one was generated, and "「 "when neither was generated.

(4) Measurement of light reflectance The obtained molded article was recorded with a self-recording spectrophotometer (manufactured by Shimadzu Corporation) equipped with a multi-purpose large sample chamber unit (manufactured by Shimadzu Corporation, trade name: MPC-2200). (Product name: UV-2400PC), the light reflectance of the cured product test piece was measured.

(5) LED conduction test (evaluation of light resistance)
A test piece of a cured product was fixed on an LED package mounted with a blue LED (product name: OBL-CH2424, manufactured by Gene Lights Co., Ltd.), and a current of 150 mA was supplied for 1 week at an ambient temperature of 60 ° C. to emit light. Then, the light irradiation surface of the LED of the cured product test piece was visually observed and evaluated according to the following criteria.
：: no discoloration ×: light irradiation surface turned brown

(7) Flexural modulus and flexural strength measurement The obtained molded product was measured for flexural modulus and flexural strength in accordance with ISO178.

(8) Evaluation of heat resistance After measuring the initial value of the light reflectance of the cured product test piece, it was heated at 180 ° C for 72 hours in an oven, and then the light reflectance of the cured product test piece after heating was measured. When the difference from the initial reflectance to the reflectance after the heat resistance test evaluation was less than 5%, it was evaluated as ○, when it was 5 or more and less than 10%, it was evaluated as Δ, and when it was 10% or more, it was evaluated as ×.

  The composition and the cured product of the present invention can be suitably used as a raw material of a reflector for an optical semiconductor light emitting device.

Reference Signs List 10 Filling device 11 Plunger 13 Flow path 14 Cooling unit 15 Needle 20 Mold 22 Fixed mold 22A Heating unit 22B Cooling unit 23 Movable mold 21 Cavity 221 Introduction path 222 Opening 223 Needle 224 Elastic member 232 Cavity 238 Elastic member 240 Decompression tube 510,610 Lead frame 520,620 Optical semiconductor element mounting substrate 521,621 Reflector 530,630 Optical semiconductor light emitting device 531,631 Optical semiconductor element 532,632 Wire 533,633 Transparent sealing resin 534,634 Phosphor

Claims (13)

It contains the following components (A) to (C) and (H), and may contain one or more selected from the group consisting of the following components (D) to (G):
A thermosetting composition having a shear viscosity at 25 ° C. of 10 s ⁻¹ at 1 Pa · s or more and 500 Pa · s or less and a shear viscosity at 25 ° C. of 100 s ⁻¹ at 0.3 Pa · s or more and 100 Pa · s or less.
(A) a substituted or unsubstituted (meth) acrylate compound having a viscosity of 1 to 300 mPa · s at 25 ° C. and having an ester-bonded substituted or unsubstituted alicyclic hydrocarbon group having 6 or more carbon atoms; (B) average primary particle size Spherical silica having a diameter of 1 to 100 μm (C) Titanium dioxide (D) (Meth) acrylic acid or a monofunctional (meth) acrylate compound having a polar group (E) Monomers other than the components (A) and (D) Functional (meth) acrylate compound (F) Polyfunctional (meth) acrylate compound other than the component (A) (G) Plate-like filler (H) Fumed silica having a particle size of 5 to 50 nm The component (A) is a (meth) acrylate compound having an adamantyl group represented by the following general formula (I), a (meth) acrylate compound having an isobornyl group represented by the following general formula (II), The heat according to claim 1, which is a (meth) acrylate compound having a norbornyl group represented by (III) or a (meth) acrylate compound having a dicyclopentanyl group represented by the following general formula (IV). Curable composition.
(In the formulas (I), (II), (III) and (IV), R ¹ each independently represents a hydrogen atom or a methyl group.
X each independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms.
U represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, or ＯO formed by combining two U atoms. k represents an integer of 1 to 15. l shows the integer of 1-8. m shows the integer of 1-11. n shows the integer of 1-15.
When there are a plurality of U in the formula, the plurality of U may be the same or different. )   3. The thermosetting composition according to claim 1, wherein the component (A) is adamantyl methacrylate, 1-norbornyl methacrylate, 1-isobornyl methacrylate, or 1-dicyclopentanyl methacrylate. 4.   The content of the component (B) is 10 to 90% by mass and the content of the component (C) is 1 to 80% by mass based on 100% by mass of the total of the components (A) to (C). The thermosetting composition according to any one of claims 1 to 3.   The (meth) acrylate compound is one or more selected from a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isobornyl group, and a substituted or unsubstituted dicyclopentanyl group. The thermosetting composition according to any one of claims 1 to 4, wherein the thermosetting composition is a (meth) acrylate compound in which an alicyclic hydrocarbon group is ester-bonded. It contains one or more components selected from the components (D) to (F),
The content of the component (A) is 1 to 80% by mass and the content of the component (B) is 10 to 90% by mass based on 100% by mass of the total of the components (A) to (F). The thermosetting composition according to any one of claims 1 to 5.   The thermosetting composition according to any one of claims 1 to 6, wherein the spherical silica has been subjected to (meth) acrylsilane surface treatment. Supplying the thermosetting composition according to any one of claims 1 to 7 into a plunger,
A step of filling the cavity in a mold with the thermosetting composition filled in the plunger, by the plunger.
Thermosetting the thermosetting composition in the cavity, and extruding the thermosetting thermosetting resin,
A method for producing a thermosetting resin comprising: The method for producing a thermosetting resin according to claim 8 , wherein the mold temperature of the cavity is 100 ° C. or more and 180 ° C. or less. In the step of filling the cavity in the mold with the plunger, the thermosetting composition filled in the plunger is filled with the thermosetting composition through a flow path temperature-controlled to 50 ° C. or less. The method for producing a thermosetting resin according to claim 8 or 9 , wherein a composition is filled in the cavity in the mold. In the step of filling the cavity in the mold by the plunger with the thermosetting composition filled in the plunger, the thermosetting composition is provided in a flow path between the plunger and the cavity. The method for producing a thermosetting resin according to any one of claims 8 to 10 , further comprising a gate system for blocking flow of heat and transfer of heat. Open the gate of the gate system, fill the cavity in the mold with the thermosetting composition,
The thermosetting increases the injection pressure of the thermosetting composition after the start of the curing, performs a holding pressure before the completion of the curing, and after the completion of the holding pressure, closes the gate of the gate system to complete the thermosetting. Item 12. The method for producing a thermosetting resin according to Item 11 . The method for producing a thermosetting resin according to claim 8 , wherein the filling step and the thermosetting step are performed within 0.2 to 3 minutes.