JP6754328B2 - Mold release recovery agent composition for transfer molding - Google Patents

Description

The present invention relates to a mold releasability recovery agent composition for transfer molding that improves continuous moldability of a silicone resin, a silicone-containing hybrid resin, or the like.

Epoxy resins are widely used for semiconductor encapsulation and optical semiconductor packages, but in recent years, resins containing silicone components have come to be widely used for the purpose of low stress, and further have high heat resistance. Silicone rubber and resins containing silicone resin as the main components, which take advantage of light resistance, have come to be used for encapsulants and reflectors using casting, compression molding, injection molding, and transfer molding.

However, the transfer molding as described above causes mold contamination due to the low molecular weight component of silicone, which is not found in conventional epoxy resins, and a mold release material and a cleaning material are required for continuous molding. .. It has been found that for mold contamination caused by the silicone component, sufficient cleaning cannot be performed by conventional cleaning sheet, melamine resin, or acrylic resin molding (Patent Documents 1 to 3). ).
In particular, in Patent Document 4, as a silicone rubber composition for mold surface release treatment, a mold release component having specific physical properties is added to the addition-curable silicone rubber composition to clean and release the mold surface. The molding method to be performed is disclosed. However, when trying to mold a resin containing a compound having a sulfur atom such as a sulfur-containing silane coupling agent added to a condensation-curable silicone resin composition, the sulfur component remaining in the flow path of the mold or the molding machine. As a result, the above-mentioned silicone rubber for mold release treatment inhibits curing, so that there is a problem that the mold cannot be cleaned by this method.

Further, although there are reports on mold release materials suitable for silicone-based rubber, there is currently no suitable material for a silicone resin composition based on a silicone resin (Patent Document 5).

JP-A-2009-209330 Japanese Unexamined Patent Publication No. 2006-007506 Japanese Unexamined Patent Publication No. 2010-173293 International Publication WO2015-151480 Japanese Unexamined Patent Publication No. 2004-082433

The present invention has been made in view of the above circumstances, and when a silicone resin, a hybrid resin containing silicone, or the like is used as the resin for transfer molding, the continuous moldability of the mold can be improved. It is an object of the present invention to provide a mold release recovery agent composition.

（式中、Ｒ^１は互いに独立に、ヒドロキシル基、炭素原子数１〜３のアルキル基、シクロヘキシル基、フェニル基、ビニル基、及びアリル基から選ばれる１価炭化水素基であり、ｍは５〜５０の整数を示す。）
（Ｃ）無機充填材：３００〜８００質量部、
（Ｄ）有機金属系縮合触媒：０．０１〜１０質量部、
（Ｅ）金属石鹸：１．０〜１０質量部、
（Ｆ）フッ素系離型剤：１．０〜１０質量部、
を含有するトランスファー成形用金型離型性回復剤組成物を提供する。 In order to solve the above problems, the present invention
(A) Condensation reaction type resin-like organopolysiloxane solid at 25 ° C .: 70 to 95 parts by mass,
(B) Organopolysiloxane having a linear diorganopolysiloxane residue represented by the following general formula (1) and containing at least one cyclohexyl group or phenyl group in one molecule: 5 to 30 parts by mass. (However, the total of the components (A) and (B) is 100 parts by mass),

(In the formula, R ¹ is a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group independently of each other, and m is 5 Indicates an integer of ~ 50.)
(C) Inorganic filler: 300 to 800 parts by mass,
(D) Organometallic condensation catalyst: 0.01 to 10 parts by mass,
(E) Metal soap: 1.0 to 10 parts by mass,
(F) Fluorine-based mold release agent: 1.0 to 10 parts by mass,
To provide a mold release recovery agent composition for transfer molding containing the above.

With such a composition, when a silicone resin, a hybrid resin containing silicone, or the like is used as the resin for transfer molding, the continuous moldability of the mold can be improved.

At this time, the condensation reaction type resin-like organopolysiloxane is preferably a resin-like organopolysiloxane represented by the following average composition formula (2) and having a polystyrene-equivalent weight average molecular weight of 1,000 to 20,000. ..
(CH ₃ ) _a Si (OR ² ) _b (OH) _c O _{(4-a-bc) / 2} (2)
(In the formula, R ² represents the same or different organic groups having 1 to 4 carbon atoms, and a, b, and c are 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0. It is a number that satisfies 001 ≦ c ≦ 0.5 and 0.801 ≦ a + b + c <2.

With such a composition containing a resin-like organopolysiloxane, the continuous moldability of the mold can be further improved when a silicone resin, a hybrid resin containing silicone, or the like is used as the resin for transfer molding.

Further, it is preferable that the transfer molding mold release recovery agent composition can be pressure-molded at room temperature.

With such a composition, the present composition can be pressure-molded at room temperature to easily improve the continuous moldability of the mold.

Further, the resin to be transfer-molded using the mold for recovering the releasability by the transfer molding mold releasability recovery agent composition may be a silicone resin or a hybrid resin containing silicone.

In the case of the mold releasability recovery agent composition for transfer molding of the present invention, even if the resin to be transferred is a silicone resin or a hybrid resin containing silicone, it is possible to suppress curing inhibition of the composition. , The continuous moldability of the mold can be improved.

In the case of the mold releasability recovery agent composition for transfer molding of the present invention, when a silicone resin or a hybrid resin containing silicone is used as the resin for transfer molding, curing inhibition of the composition does not occur and the mold is used. The continuous moldability of the above can be improved.

It is the schematic of the molded article used for the continuous moldability test of Examples and Comparative Examples.

As described above, when a silicone resin, a hybrid resin containing silicone, or the like is used as the resin for transfer molding, the mold releasability recovery agent composition for transfer molding can improve the continuous moldability of the mold. Development was required.

As a result of diligent studies on the above problems, the present inventor has found that a composition containing a specific condensation reaction type silicone resin and in combination with a specific release agent can achieve the above problems, and the present invention has been developed. I came to the point.

（式中、Ｒ^１は互いに独立に、ヒドロキシル基、炭素原子数１〜３のアルキル基、シクロヘキシル基、フェニル基、ビニル基、及びアリル基から選ばれる１価炭化水素基であり、ｍは５〜５０の整数を示す。）
（Ｃ）無機充填材：３００〜８００質量部、
（Ｄ）有機金属系縮合触媒：０．０１〜１０質量部、
（Ｅ）金属石鹸：１．０〜１０質量部、
（Ｆ）フッ素系離型剤：１．０〜１０質量部、
を含有するトランスファー成形用金型離型性回復剤組成物である。 That is, the present invention is
(A) Condensation reaction type resin-like organopolysiloxane solid at 25 ° C .: 70 to 95 parts by mass,
(B) Organopolysiloxane having a linear diorganopolysiloxane residue represented by the following general formula (1) and containing at least one cyclohexyl group or phenyl group in one molecule: 5 to 30 parts by mass. (However, the total of the components (A) and (B) is 100 parts by mass),

(In the formula, R ¹ is a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group independently of each other, and m is 5 Indicates an integer of ~ 50.)
(C) Inorganic filler: 300 to 800 parts by mass,
(D) Organometallic condensation catalyst: 0.01 to 10 parts by mass,
(E) Metal soap: 1.0 to 10 parts by mass,
(F) Fluorine-based mold release agent: 1.0 to 10 parts by mass,
It is a mold releasability recovery agent composition for transfer molding containing.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

The mold release recovery agent composition for transfer molding of the present invention contains the components (A) to (F) as described above. Hereinafter, each component will be described.

<(A) Condensation reaction type resin-like organopolysiloxane>
The component (A) is a condensation reaction type resin-like organopolysiloxane that is solid at 25 ° C., and has a crosslinked structure with the organopolysiloxane of the component (B) in the presence of the organometallic condensation catalyst of the component (D) described later. Is what forms. Here, "resin-like" means that the organopolysiloxane has a branched or three-dimensional network structure.

The resin-like organopolysiloxane of the component (A) is not particularly limited as long as it causes a condensation reaction. As described above, since the mold release recovery agent composition of the present invention is composed of a condensation reaction type silicone resin, it is cured even when a resin containing a component that inhibits the addition reaction is transfer molded. Inhibition can be prevented.

The condensation-reactive resin-like organopolysiloxane of the component (A) is represented by, for example, the following average composition formula (2), and is a polystyrene-equivalent weight average obtained by gel permeation chromatography (GPC) using tetrahydrofuran or the like as a developing solvent. Examples thereof include resin-like organopolysiloxane having a molecular weight of 1,000 to 20,000.
(CH ₃ ) _a Si (OR ² ) _b (OH) _c O _{(4-a-bc) / 2} (2)
(In the formula, R ² represents the same or different organic groups having 1 to 4 carbon atoms, and a, b, and c are 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0. It is a number that satisfies 001 ≦ c ≦ 0.5 and 0.801 ≦ a + b + c <2.

In the above average composition formula (2), a indicating the content of the methyl group is 0.8 ≦ a ≦ 1.5, preferably 0.8 ≦ a ≦ 1.2, and more preferably 0.9 ≦ a ≦. It is 1.1. A composition containing a resin-like organopolysiloxane having a of 0.8 or more does not make the cured product too hard and has good crack resistance. On the other hand, when a is 1.5 or less, the obtained resin-like organopolysiloxane tends to solidify.

In the above average composition formula (2), b indicating the content of the alkoxy group is 0 ≦ b ≦ 0.3, preferably 0.001 ≦ b ≦ 0.2, and more preferably 0.01 ≦ b ≦ 0. It is 1. When b is 0.3 or less, the molecular weight of the obtained resin-like organopolysiloxane is appropriate, and the crack resistance does not decrease.

In the above average composition formula (2), c indicating the content of the hydroxyl group bonded to the Si atom is 0.001 ≦ c ≦ 0.5, preferably 0.01 ≦ c ≦ 0.3, and more preferably 0. .05 ≦ c ≦ 0.2. When c is 0.5 or less, the obtained resin-like organopolysiloxane exhibits appropriate hardness by a condensation reaction during heat curing, and becomes a cured product having good crack resistance. On the other hand, when c is 0.001 or more, the obtained resin-like organopolysiloxane does not have an excessively high melting point and is excellent in workability. In order to control the value of c to 0.001 ≦ c ≦ 0.5, it is preferable to set the complete condensation rate of the raw material to 86 to 96%. If the complete condensation rate is 86% or more, the value of c is 0.5 or less and the melting point is not too low, and if it is 96% or less, the value of c is 0.001 or more and the melting point is too high. Absent.
Here, the complete condensation rate indicates the ratio of the number of moles in which all the alkoxy groups contained in one molecule are subjected to the condensation reaction to the total number of moles of the raw material.

From the above, in the above average composition formula (2), the range of a + b + c is preferably 0.9 ≦ a + b + c ≦ 1.8, more preferably 1.0 ≦ a + b + c ≦ 1.5.

In the above average composition formula (2), R ² is an organic group having 1 to 4 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group and an isopropyl group, so that raw materials can be easily obtained. Therefore, a methyl group or an isopropyl group is preferable.

The resin-like organopolysiloxane of the component (A) preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 1,500 to 10,000, more preferably 1,500 to 10,000, as converted by a polystyrene standard measured by GPC. Is 2,000 to 8,000. When the molecular weight is 1,000 or more, the obtained resin-like organopolysiloxane is easily solidified, and when the molecular weight is 20,000 or less, the obtained composition becomes too viscous and the fluidity decreases. There is no risk and the moldability is good.
The weight average molecular weight referred to in the present invention refers to a weight average molecular weight using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min
Detector: RI
Column: TSK-GEL H type (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 5 μL

The resin-like organopolysiloxane represented by the above average composition formula (2) generally has a Q unit (SiO _4/2 ), a T unit (CH ₃ SiO _3/2 ), and a D unit ((CH ₃ ) ₂ SiO _{2 /.} It can be expressed by a combination of ₂ ) and M unit ((CH ₃ ) ₃ SiO _1/2 ). When the resin-like organopolysiloxane is represented by this expression method, the ratio of the content of T units to the total number of all siloxane units is preferably 70% or more (70 to less than 100%), preferably 75%. It is more preferably more than (75 to less than 100%), and particularly preferably 80% or more (less than 80 to 100%). When the ratio of the content of T units is 70% or more, the overall balance of hardness, adhesion, appearance, etc. of the obtained cured product is good. The balance may be in M, D, or Q units, and the ratio of the total of these units to all siloxane units is 30% or less (0 to 30%), particularly more than 0% and 30% or less, that is, The T unit is preferably less than 100%.

The resin-like organopolysiloxane represented by the average composition formula (2) can be obtained as a hydrolyzed condensate of the silane compound represented by the following general formula (3).
(CH ₃ ) _n SiX _4-n (3)
(In the formula, X represents a halogen atom such as chlorine or an alkoxy group having 1 to 4 carbon atoms, and n is any of 0, 1, and 2.)
In this case, X is preferably a chlorine atom or a methoxy group from the viewpoint of obtaining a solid organopolysiloxane at 25 ° C.

Examples of the silane compound represented by the above formula (3) include organotrichlorosilane such as methyltrichlorosilane; organotrialkoxysilane such as methyltrimethoxysilane and methyltriethoxysilane; and dimethyldimethoxysilane and dimethyldiethoxysilane. Examples thereof include diorganodialkoxysilane; tetrachlorosilane; tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane.

The hydrolysis and condensation of the above-mentioned silane compound having a hydrolyzable group may be carried out by a usual method, but is preferably carried out in the presence of a catalyst. As this catalyst, either an acid catalyst or an alkali catalyst can be used. For example, the acid catalyst is preferably an organic acid catalyst such as acetic acid, an inorganic acid catalyst such as hydrochloric acid or sulfuric acid, and the alkali catalyst is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or tetramethylammonium hydroxide. And other organic alkaline catalysts are preferred. More specifically, when a silane containing a chloro group is used as the hydrolyzable group, a hydrolyzed condensate having an appropriate molecular weight is used as a catalyst by using hydrogen chloride gas and hydrochloric acid generated by water addition as catalysts. Can be obtained.

The amount of water used for hydrolysis and condensation is generally 0 with respect to 1 mol of the total amount of hydrolyzable groups (eg, chloro groups) in the silane compound having hydrolyzable groups. It is 9.9 to 1.6 mol, preferably 1.0 mol to 1.3 mol. When this addition amount satisfies the range of 0.9 to 1.6 mol, the obtained composition tends to have excellent workability, and the cured product tends to have excellent toughness.

The silane compound having a hydrolyzable group is usually preferably hydrolyzed in an organic solvent such as alcohols, ketones, esters, cellosolves, and aromatic compounds. Specifically, for example, alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol, and 2-butanol, or aromatic compounds such as toluene and xylene are preferable, and the curability and curability of the obtained composition and It is more preferable to use isopropyl alcohol, toluene, or a combination of isopropyl alcohol and toluene in that the cured product has excellent toughness.

The reaction temperature for hydrolysis and condensation is preferably 10 to 120 ° C, more preferably 20 to 80 ° C. When the reaction temperature satisfies the above range, a solid hydrolyzed condensate that is difficult to gel and can be used in the next step is obtained.

The resin-like organopolysiloxane of the component (A) is preferably blended in an amount of 8.0 to 30% by mass, particularly 8.5 to 20% by mass, in the mold release recovery agent composition for transfer molding of the present invention. Further, it is preferable to add 9.0 to 18% by mass.

（式中、Ｒ^１は互いに独立に、ヒドロキシル基、炭素原子数１〜３のアルキル基、シクロヘキシル基、フェニル基、ビニル基、及びアリル基から選ばれる１価炭化水素基であり、ｍは５〜５０の整数を示す。） <(B) Organopolysiloxane>
The mold releasability recovery agent composition for transfer molding of the present invention has the following components (B) in order to reduce stress during demolding of pressure molding at room temperature and demolding from the mold. It contains an organopolysiloxane having a linear diorganopolysiloxane residue represented by the general formula (1) and containing at least one cyclohexyl group or phenyl group in one molecule.

(In the formula, R ¹ is a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group independently of each other, and m is 5 Indicates an integer of ~ 50.)

In the above formula (1), R ¹ is a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group independently of each other. It is preferably a methyl group or a phenyl group. m is an integer of 5 to 50, preferably 8 to 40, more preferably 10 to 35. If m is less than 5, the obtained cured product will have poor crack resistance. On the other hand, if m exceeds 50, the mechanical strength of the obtained cured product may be insufficient, or the viscosity may become too high, causing molding defects.

Component (B), in addition to the continuous D units form a linear diorganopolysiloxane residue represented by the formula (1) _^(R 1 _{2 SiO 2/2),} corresponding to the formula (1) It may include D units (R ₂ SiO _2/2 ), M units (R ₃ SiO _1/2 ), and / or T units (RSiO _3/2 ). The ratio of D unit: M unit: T unit is 90 to 24:75 to 9:50 to 1, especially 70 to 28:70 to 20:10 to 2 (however, the total of these units is 100). This is preferable from the viewpoint of cured product characteristics. Here, R represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a vinyl group, or an allyl group. In addition to these, component (B) may contain Q units (SiO _4/2 ). The organopolysiloxane of the component (B) is a D unit (R ¹ ₂ SiO _2/2 ) of the formula (1), a D unit (R ₂ SiO _2/2 ) that does not correspond to the formula (1), and an M unit (R ₃ ). It has at least one cyclohexyl group or phenyl group in one molecule in SiO _1/2 ) and / or T unit (RSiO _3/2 ).

In the molecule, 30% or more (for example, 30 to 90%), particularly 50% or more (for example, 50 to 80%) of the D unit present in the organopolysiloxane of the component (B) is the above general formula (for example, 30 to 90%). preferably forms a continuous D units represented by ^{_{1) (R 1 2 SiO 2/2}} ). The polystyrene-equivalent weight average molecular weight of the component (B) by gel permeation chromatography (GPC) is preferably 3,000 to 120,000, more preferably 10,000 to 100,000. When the molecular weight is in this range, the component (B) is in a solid or semi-solid state, which is suitable from the viewpoint of workability, curability and the like of the obtained composition.

The component (B) can be synthesized by combining the compounds as raw materials for each of the above units so as to have a required molar ratio in the produced polymer, and hydrolyzing and condensing in the presence of an acid, for example. ..

As raw materials for T unit (RSiO _3/2 ), trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, cyclohexyltrichlorosilane, and trimethoxy corresponding to each of these trichlorosilanes. Examples of alkoxysilanes such as silanes can be given.

（式中、ｐ＝３〜４８の整数（平均値）、ｑ＝０〜４８の整数（平均値）、かつｐ＋ｑが３〜４８（平均値）であり、各繰返し単位はブロックであってもランダムであってもよい。） As the raw material of the continuous D units (R 1 ² _{SiO 2/2)} form a linear diorganopolysiloxane residue of formula (1) include the following silane compounds.

(In the formula, p = 3 to 48 integers (average value), q = 0 to 48 integers (average value), and p + q is 3 to 48 (average value), even if each repetition unit is a block. It may be random.)

In addition, as raw materials for M units and D units that do not correspond to the above formula (1), Me ₂ PhSiCl, Me ₂ ViSiCl, Ph ₂ MeSiCl, Ph ₂ ViSiCl, Me ₂ SiCl ₂ , MeEtSiCl ₂ , ViMeSiCl _2, Ph ₂ Mono or dichlorosilanes such as SiCl ₂ and PhMeSiCl ₂ , and mono or dialkoxysilanes such as mono or dimethoxysilanes corresponding to each of these chlorosilanes can be exemplified. Here, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, and Vi is a vinyl group.

The component (B) can be obtained by combining these raw material compounds at a predetermined molar ratio and reacting them as follows, for example. Phenylmethyldichlorosilane, phenyltrichlorosilane, chlordimethylsilicone oil at both ends with 21 Sis, and toluene are added and mixed, and the mixed silane is added dropwise to the solution and co-hydrolyzed at 30 to 50 ° C. for 1 hour. Then, after aging at 50 ° C. for 1 hour, water is added for washing, azeotropic dehydration or polymerization using ammonia or the like as a catalyst is performed at 25 to 40 ° C., filtration and decompression stripping are performed.

The blending amount of the component (B) is such that the mass ratio of the component (A) to the component (B) is in the range of 95: 5 to 70:30, preferably in the range of 90: 10 to 80:20. If the blending amount of the component (B) is less than the above range, stress may be applied when the obtained composition is removed from the mold, and the molded product may be cracked. On the other hand, if the blending amount of the component (B) is larger than the above range, the viscosity of the obtained composition tends to increase, which may hinder molding.

<(C) Inorganic filler>
The inorganic filler of the component (C) is blended to increase the hardness of the mold release recovery agent composition for transfer molding of the present invention at room temperature and to improve the fluidity. As the inorganic filler of the component (C), a material usually blended in a silicone resin composition or an epoxy resin composition can be used. Examples thereof include silicas such as spherical silica, fused silica, and crystalline silica, silicon nitride, aluminum nitride, boron nitride, glass fiber, glass particles, and antimony trioxide. Among them, cost and flow. Spherical silica is desirable from the viewpoint of sex.

The average particle size of the inorganic filler is preferably 5 to 40 μm, particularly preferably 7 to 35 μm. When the average particle size is 5 μm or more, appropriate viscosity and fluidity can be obtained, and there is no possibility that the transmittance will decrease. When the average particle size is 40 μm or less, the generation of burrs is suppressed and there is no risk of soiling the mold. As the inorganic filler having an average particle size of 5 to 40 μm, a commercially available one may be used, or it can be produced by a known method. In order to make the silicone resin composition highly fluid, it is preferable to use a combination of a fine region of 0.1 to 3 μm, a medium particle size region of 4 to 8 μm, and a coarse region of 10 to 50 μm. The average particle size was obtained as the cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser light diffraction method.

The blending amount of the inorganic filler as the component (C) is 300 to 800 parts by mass, particularly preferably 400 to 700 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending amount is less than 300 parts by mass, resin bleeds derived from the components (A) and (B) may be generated to stain the mold, and if it exceeds 800 parts by mass, unfilling defects due to thickening or unfilling defects may occur. Due to the loss of flexibility, unfilling may occur, and the effect of improving continuous moldability may not be obtained for the entire mold. The blending amount of the inorganic filler as the component (C) is preferably in the range of 10 to 90% by mass, particularly 50 to 85% by mass of the entire composition.

<(D) Organometallic condensation catalyst>
The organometallic condensation catalyst of the component (D) is a condensation catalyst for use in curing the organopolysiloxane of the components (A) and (B), and the stability of the components (A) and (B) and the coating film. It is selected in consideration of hardness, curability, etc. Specifically, for example, zinc organic acid, Lewis acid catalyst, organic aluminum compound, organic titanium compound and the like are preferably used, and more specifically, zinc benzoate, zinc octylate, p-tert-butylbenzoic acid and the like are preferably used. Zinc, zinc laurate, zinc stearate, aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum triisopropoxide, aluminum acetylacetonate, ethylacetate acetate aluminum di (n-butylate), aluminum- Examples thereof include organic metal condensation catalysts such as n-butoxydiethylacetate acetate, tetrabutyl titanate, tetraisopropyl titanate, tin octylate, cobalt naphthenate, and tin naphthenate. Above all, the use of zinc benzoate is preferable.
Organic compound-based condensation catalysts such as basic organic compounds and acidic organic compounds are not preferable for use because of their poor storage stability.

The blending amount of the organometallic condensation catalyst is 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the organopolysiloxanes of the components (A) and (B). It is 5 parts by mass. When the blending amount is out of the above range, the curability of the obtained composition is lowered and the stability is poor.

<(E) Metal soap>
The metal soap of the component (E) contains a silicone resin or silicone by exuding to the surface of the molded product during molding of the mold release recovery agent composition for transfer molding of the present invention and transferring to the mold. It is blended to improve the releasability of hybrid resins and the like during molding. The metal soap referred to here is generally a combination of a long-chain fatty acid and a metal ion, and a non-polar or low-polarity portion based on the fatty acid and a polar portion based on the bond portion with the metal are combined in one molecule. You can use it if you have it. Examples of the long-chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids.

Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and further, from the viewpoint of high releasability effect, 6 to 18 carbon atoms are preferable. Saturated fatty acids are more preferred. Examples of the metal ion include zinc, cobalt, aluminum, strontium and the like, in addition to alkali metals and alkaline earth metals. Specifically, lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, sodium laurate, sodium oleate, Sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, magnesium laurate, oleic acid Magnesium, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate, calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate , Zinc 12-hydroxystearate, zinc laurate, zinc oleate, zinc 2-ethylhexanoate, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, barium ricinol Is exemplified. Among these metal soaps, metal stearic acid salts are preferable because they are easily available, have high safety, and have high industrial feasibility. Further, these may be used alone or in combination of two or more.

The blending amount of the metal soap is 1.0 to 10 parts by mass, preferably 1.2 to 8.0 parts by mass, based on 100 parts by mass of the total of the organopolysiloxanes of the components (A) and (B). , Particularly preferably 2.0 to 6.0 parts by mass. If the blending amount is less than 1.0 part by mass, sufficient releasability cannot be obtained, and if it is more than 10 parts by mass, the metal soap tends to seize on the mold, and conversely, the releasability may decrease. ..

<(F) Fluorine-based mold release agent>
Similar to the metal soap of the component (E), the fluorine mold release agent of the component (F) exudes to the surface of the molded product during molding of the mold release property recovery agent composition for transfer molding of the present invention, and the mold By shifting to, the silicone resin, the hybrid resin containing silicone, and the like are blended in order to improve the releasability at the time of molding. By using these components (E) and (F) in combination, a higher continuous moldability improving effect is exhibited as compared with the case where each of them is used alone.

The fluorine-based release agent is not particularly limited, and is a fluororesin such as polytetrafluoroethylene (PTFE), perfluoropolyether oil, a nonionic surfactant modified with a perfluoroalkyl group, and per. Examples thereof include poly (meth) acrylate having a (meth) acrylate modified with a fluoroalkyl group and a perfluoropolyether group as a polymerization unit, and commercially available products may be used. Specific examples include MR W-6823-AL, MR W-6833-AL, MR W-6846-AL, MR W-6881-AL, MR F-6441-AL, MR F-6711-AL, and MR F-. 6758-AL, MR F-681-AL, MR EF-6521-AL, MR K-6714-AL, MR X-6712-AL (all manufactured by AGC Seichemical Co., Ltd.), GW-200, GW-201, GW -250, GW-251, GW-280, GF-500, GF-501, GF-550, GF-350, MS-600, GA-3000, GA-7500, GA-7550, GA-7550B, GA-7550C , FB-961, FB-962 (all manufactured by Daikin Industries, Ltd.) and the like, and among them, solvent-free ones such as FB-961 and FB-962 are preferable.

The blending amount of the component (F) is 1.0 to 10.0 parts by mass, particularly preferably 1.2 to 8.0 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). .. If the blending amount is less than 1.0 part by mass, the mold releasability to the mold may not be sufficient, and if it exceeds 10.0 parts by mass, it may cause mold stains.

<Other additives>
Various additives can be further added to the transfer molding mold release recovery agent composition of the present invention, if necessary. For example, for the purpose of improving the properties of the resin, such as organopolysiloxane, silicone powder, silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, carbon black and titanium black other than the components (A) and (B). Black pigment can be added and blended according to the purpose.

(Manufacturing method of mold release recovery agent composition)
As a method for producing the mold release recovery agent composition for transfer molding of the present invention, an organopolysiloxane, an inorganic filler, an organic metal-based condensation catalyst, a metal soap, a fluorine-based mold release agent, and other additives are prescribed. After blending in the composition ratio of, and mixing this sufficiently uniformly with a mixer or the like, melt-mixing treatment is performed using a heat roll, a kneader, an extruder, etc., then cooled and solidified, and pulverized to an appropriate size. It can be used as a molding material for a mold release recovery agent composition.

(Forming method of mold release recovery agent composition)
The mold releasability recovery agent composition for transfer molding of the present invention is molded in a mold for molding a silicone resin or the like to transfer the mold release component in the composition to the mold and mold release. It is possible to improve the properties and continuous moldability. The above-mentioned mold release recovery agent composition is generally used in a transfer molding method, but can also be applied to an injection molding method or the like. The molding conditions of the above composition in the transfer molding method are a molding pressure of 5 to 20 N / mm ² , a molding temperature of 120 to 190 ° C., a molding time of 60 to 500 seconds, and particularly a molding temperature of 150 to 185 ° C. using a transfer molding machine. The molding time is preferably 30 to 180 seconds.

Further, it is preferable that the mold releasability recovery agent composition for transfer molding of the present invention can be pressure-molded at room temperature. With such a composition, the mold releasability and continuous moldability can be easily improved by pressure molding the composition at room temperature.

The resin to be transfer-molded by the mold treated with the mold releasability recovery agent composition of the present invention may be a silicone resin or a hybrid resin containing silicone. As described above, since the mold release recovery agent composition of the present invention is composed of a condensation reaction type organopolysiloxane, it suppresses curing inhibition by the components contained in the silicone resin and the silicone-containing hybrid resin. The continuous formability of the mold can be improved. Therefore, even a silicone resin or a hybrid resin containing silicone, which is difficult to clean the mold, can be selected as the resin for transfer molding.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Me is a methyl group, Ph is a phenyl group, and Vi is a vinyl group.

The raw materials used in Examples and Comparative Examples are shown below.
In the following, the weight average molecular weight is measured by GPC under the following measurement conditions.
<Molecular weight measurement conditions>
Developing solvent: tetrahydrofuran Flow rate: 0.35 mL / min
Detector: RI
Column: TSK-GEL H type (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 5 μL

(A) Synthesis of resin-like organopolysiloxane [Synthesis Example 1]
100 parts by mass of methyltrichlorosilane and 200 parts by mass of toluene were placed in a 1 L flask, and a mixed solution of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise in the liquid under ice cooling. The mixture was added dropwise over an internal temperature range of −5 to 0 ° C. over 5 hours, then heated and stirred at the reflux temperature for 20 minutes. Then, the mixed solution was cooled to room temperature, 12 parts by mass of water was added dropwise at 30 ° C. or lower for 30 minutes, and the mixture was stirred for 20 minutes. After 25 parts by mass of water was added dropwise thereto, the obtained reaction mixture was stirred in the range of 40 to 45 ° C. for 60 minutes. Then, 200 parts by mass of water was added to the reaction mixture to separate the organic layer. The organic layer is washed to neutrality, then azeotropically dehydrated, filtered, and stripped under reduced pressure to form a colorless and transparent solid represented by the following average formula (A-1) (melting point 75 ° C., weight average molecular weight 3). 36.0 parts by mass of a resin-like organopolysiloxane (A-1) of 000) was obtained.
(CH ₃ ) _1.0 Si (OC ₃ H ₇ ) _0.07 (OH) _0.10 O _1.4 (A-1)

(B) Synthesis of organopolysiloxane [Synthesis Example 2]
Phenylmethyldichlorosilane 100 g (4.4 mol%), phenyltrichlorosilane 2,100 g (83.2 mol%), dimethylpolysiloxane oil with 21 Sis and both terminal chloroblocks 2,400 g (12.4 mol%) ), 3,000 g of toluene was mixed, and the above-mentioned silane mixed in 11,000 g of water was added dropwise, and co-hydrolyzed in the range of 30 to 50 ° C. for 1 hour. Then, it was aged at 30 ° C. for 1 hour, washed with water, and then azeotropically dehydrated, filtered, and stripped under reduced pressure to obtain a colorless and transparent product (organosiloxane (B-1)). The siloxane (B-1) had a melt viscosity of 5 Pa · s at 150 ° C. using an ICI cone plate, and had a weight average molecular weight of 50,000.
[(Me ₂ SiO) ₂₁ ] _0.124 (PhMeSiO) _0.044 (PhSiO _1.5 ) _0.832 (B-1)

(C) Inorganic filler (C-1): fused spherical silica (MAR-T815 / 53C, average particle size 10 μm, manufactured by Ryumori Co., Ltd.)

(D) Organometallic condensation catalyst (D-1): Zinc benzoate (manufactured by Wako Pure Chemical Industries, Ltd.)

(E) Metal soap (E-1): Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.)

(F) Fluorine-based mold release agent (F-1): Fluorine-based mold release agent for internal addition (Die-free FB961, manufactured by Daikin Corporation)

(G) Other mold release agent (G-1): Hardened castor oil (Kao Wax 85P, manufactured by Kao Corporation)
(G-2): Carnauba mold release agent (TOWAX-131, manufactured by Toa Kasei Co., Ltd.)
(G-3): Fatty acid ester release agent (SL-900A, manufactured by RIKEN Vitamin Co., Ltd.)

[Examples 1 to 3 and Comparative Examples 1 to 9]
Each component shown above was mixed with a hot double roll in the formulation (parts by mass) shown in Tables 1 to 3, cooled and pulverized to obtain a mold release recovery agent composition. The following characteristics were measured for these compositions. The results are shown in Tables 1-3.

(Continuous moldability test)
As shown in FIG. 1, the resin composition (mold releasability recovery agent composition) 101 shown in Tables 1 to 3 and the copper lead frame 102 whose entire surface is silver-plated are used under the following molding conditions. , The composition was transferred three times to acclimatize the surface of the mold.
Molding temperature: 175 ° C
Molding pressure: 100 N / mm ²
Molding time: 180 seconds

Subsequently, a continuous moldability test was conducted under the following molding conditions using a white silicone resin (trade name: SWC-7000, manufactured by Shin-Etsu Chemical Co., Ltd.) and a copper lead frame 102 whose entire surface was silver-plated. .. Continuous transfer molding is performed until the white reflector portion on the matrix type concave reflector substrate 10 adheres to the mold and causes a shape defect, or sticks to the mold and continuous molding becomes impossible, and the surface condition of the mold is also changed. confirmed. The maximum number of continuous moldings was 100. In FIG. 1, 100 indicates an individualized concave reflector substrate.
Molding temperature: 175 ° C
Molding pressure: 100 N / mm ²
Molding time: 60 seconds

As shown in Table 1, by treating the mold with the mold release recovery agent composition of the present invention (Examples 1 to 3), the silicone resin can be continuously molded nearly 100 times. The continuous moldability of the mold could be improved.
On the other hand, as shown in Tables 2 and 3, in Comparative Examples 1 and 2 containing only one of the component (E) and the component (F) as the mold release component, the resin was put on the mold during the continuous molding test. Adhesion and baking occurred, and continuous molding could be performed less than in the examples. Further, in Comparative Example 3 containing no organopolysiloxane as the component (B), a plurality of places were taken in the molded product, the resin adhered to the mold, and the molded product could be continuously molded only 10 times. Further, in Comparative Examples 4 to 6 in which other mold release agents were used instead of the component (F), resin adhered to the mold and baking occurred, and continuous molding could be performed less than in the examples. It was. Further, even in Comparative Examples 7 to 9 in which other mold release agents are used instead of the component (E), resin adheres to the mold and baking occurs, and continuous molding can be performed less than in the examples. There wasn't.

[Comparative Example 10]
Average composition formula: 64.5 parts by mass of polyorganosiloxane represented by Vi _0.002 Me _1.998 SiO _1,000 , 32.2 parts of fumed silica, and bi-terminal silanol groups having a viscosity of 60 mm ² / s as a plasticizing agent. A hydrogen siloxane represented by an average unit formula: Me ₃ SiO (Me ₂ SiO) ₃ (MeHSiO) ₅ SiMe ₃ with respect to a rubber base obtained by heating, melting and mixing 3.3 parts of sealed dimethylsiloxane with a kneader. 1.2 parts, 0.05 part of isopropyl alcohol solution of chloroplatinic acid having a platinum content of 1% by weight, 5 parts of calcium stearate, 5 parts of die-free FB961 which is a fluorine-based mold release agent for internal addition, Me ₃ SiO (Me ₂₎ SiO) 2 parts of dimethylsiloxane composed of ₆₀₀ SiMe ₃ and 0.01 part of 1-ethynyl-cyclohexanol were added and mixed with two rolls to prepare a sheet having a thickness of 3 mm.
Place 10 g of this sheet on the reflector molds used in Examples 1 to 3 and Comparative Examples 1 to 9, and perform compression molding at 150 ° C. for 5 minutes at a pressure of 80 N / mm ² to restore mold releasability. However, the result was that the curing was sweet due to the component that inhibits the addition reaction by the platinum catalyst derived from the white silicone resin component, and the rubber compound adhered to the mold.

From these results, in the case of the mold release property recovery agent composition for transfer molding of the present invention, by using a condensation type resin-like organopolysiloxane, curing inhibition is suppressed, and further, two specific types of release are obtained. It was clarified that the continuous moldability can be significantly improved by using the mold agent together. From the above, it was shown that this mold release recovery agent composition is useful.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

10: Concave reflector substrate 100: Individualized concave reflector substrate 101: Resin composition 102: Lead frame

Claims (4)

(A) Condensation reaction type resin-like organopolysiloxane solid at 25 ° C .: 70 to 95 parts by mass,
(B) Organopolysiloxane having a linear diorganopolysiloxane residue represented by the following general formula (1) and containing at least one cyclohexyl group or phenyl group in one molecule: 5 to 30 parts by mass. (However, the total of the components (A) and (B) is 100 parts by mass),

(In the formula, R ¹ is a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group, and an allyl group independently of each other, and m is 5 Indicates an integer of ~ 50.)
(C) Inorganic filler: 300 to 800 parts by mass,
(D) Organometallic condensation catalyst: 0.01 to 10 parts by mass,
(E) Metal soap: 1.0 to 10 parts by mass,
(F) Fluorine-based mold release agent: 1.0 to 10 parts by mass,
A mold releasability recovery agent composition for transfer molding, which is characterized by containing. A claim that the condensation reaction type resin-like organopolysiloxane is represented by the following average composition formula (2) and has a polystyrene-equivalent weight average molecular weight of 1,000 to 20,000. Item 2. The mold releasability recovery agent composition for transfer molding according to Item 1.
(CH ₃ ) _a Si (OR ² ) _b (OH) _c O _{(4-a-bc) / 2} (2)
(In the formula, R ² represents the same or different organic groups having 1 to 4 carbon atoms, and a, b, and c are 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0. It is a number that satisfies 001 ≦ c ≦ 0.5 and 0.801 ≦ a + b + c <2. The mold releasability recovery agent composition for transfer molding according to claim 1 or 2, wherein the mold releasability recovery agent composition for transfer molding can be pressure-molded at room temperature. .. Claim 1 is characterized in that the resin to be transfer-molded using the mold for recovering the mold releasability by the transfer molding mold releasability recovery agent composition is a silicone resin or a hybrid resin containing silicone. The mold releasability recovery agent composition for transfer molding according to any one of 3 to 3.

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