TW201538638A - Addition-cured silicone composition - Google Patents

Abstract

Provided is an addition-cured silicone composition such that the obtained silicone cured product is superior with respect to adhesiveness and appearance, and has little contraction or change in hardness due to heat. The addition-cured silicone composition contains: (A) 100 parts by mass of a polyorganosiloxane having an alkenyl group; (B) a polyorganohydrogensiloxane at an amount such that there are 0.9-3.0 moles of hydrogen atoms bonded to silicon atoms for every total of 1 mole of alkenyl groups that component (A) has; (C) a catalytic amount of a hydrosilylation catalyst; (D) 0.01-10 parts by mass of an adhesiveness imparting agent; and (E) 0.001-0.05 parts by mass of an organic free radical (compound having a 5- or 6-membered nitrogen-containing heterocyclic skeleton and of which the nitrogen atoms are bonded to the oxygen atoms of the free radicals).

Description

Addition hardening polyfluorene composition

The present invention relates to an addition-curable polyfluorene-oxygen composition, and particularly relates to an addition-curable polyfluorene-oxygen composition which has excellent adhesion and appearance with respect to the obtained cured product, and which has little change in heat shrinkage and hardness.

A polyfluorene oxide (polyorganotoxime) composition such as a polyoxyxene rubber or a polyoxymethylene gel is an excellent cured product because of various properties such as weather resistance, heat resistance, hardness, and elongation. Used in a variety of uses.

For example, in an optical semiconductor device including a light-emitting element such as a light-emitting diode (LED), a material of a sealed light-emitting device is a polymerized polyoxygen composition having excellent heat resistance and ultraviolet resistance. In particular, the addition-hardening polyoxonium composition which is hardened by hydrosilylation can be hardened by heating for a short period of time, and is not widely used as a by-product at the time of hardening, and is widely used.

Further, compared with the epoxy resin, since the adhesion of the addition-curable polyfluorene-oxygen composition is low, the adhesion is improved, and it has been proposed to formulate an alkoxyalkyl group and/or in the above composition. Epoxy group, with An isomeric cyanuric acid derivative having a crosslinkable vinyl group and/or a hydrogenated alkylene group (for example, refer to Patent Document 1).

However, when the adhesion-improving component is blended in the addition-curable polyfluorene-oxygen composition, the obtained cured product may be caused by cracking during heating due to the component, or may be generated therefrom. The case where the adhesive is peeled off. This is believed to be caused by the simultaneous multiplication of the shrinkage of the heated cured product and the change in hardness. Therefore, development of an addition-curable polyfluorene-oxygen composition capable of imparting an adhesion-promoting component capable of sufficiently ensuring an improvement in adhesion while suppressing the cause of the composition is desired. The shrinkage of the cured product and the change in hardness.

On the other hand, in order to suppress the change in the hardness of the heat, a technique of formulating a rare earth salt of a carboxylic acid in an addition-curable polyfluorene-oxygen composition which does not contain the above-mentioned adhesion-promoting component is proposed (for example, reference) Patent Document 2). However, the following attempts have not been made: in the addition-hardening polyoxon composition in which the adhesion-promoting component is formulated, the addition-hardening polyoxon composition hardening due to the adhesion-improving component is suppressed. The heat of the object shrinks.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-065161

[Patent Document 2] International Publication No. 2013/084699

The present invention is an invention capable of solving such a problem, and is intended to provide an additive-hardening polyfluorene-oxygen composition having excellent adhesion and appearance while being subjected to heat shrinkage and hardness change. .

The addition-hardening polyfluorene oxide composition of the present invention is characterized in that: (A) a polyorganosiloxane having at least one alkenyl group bonded to a ruthenium atom in one molecule: 100 parts by mass; (B) a polyorganohydrohydroxane having at least two hydrogen atoms bonded to a halogen atom in one molecule: for the total amount of alkenyl groups of the above-mentioned (A) component, 1 mole is bonded to a germanium atom The hydrogen atom is in an amount of 0.9 to 3.0 moles; (C) the hydrogenation oximation reaction catalyst: the amount of the catalyst; (D) at least one selected from the following (D1) and (D2) as the adhesion imparting agent: 0.01 to 10 parts by mass, (D1) having at least one selected from the group consisting of an epoxy group and an alkoxyalkyl group, and an isocyanuric acid derivative selected from at least one selected from the group consisting of a hydrogenated alkyl group and a crosslinkable vinyl group. (D2) having at least one selected from the group consisting of an epoxy group and an alkoxy group, but not having a hetero-cyanuric acid ring, or a decane compound; and (E) represented by the following general formula (3) Organic radicals: 0.001 to 0.05 parts by mass,

(In the formula (3), R ⁵ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; and R ⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxyl group or a hydroxyl group, or is bonded to the same Two R ^{6 of} carbon atoms represent =0, but at least one of R ⁶ is a carboxyl group or a hydroxyl group, or formula (3) has at least one of two R ⁶ bonded to the same carbon atom. O).

According to the present invention, it is possible to provide an addition-hardening polyfluorene-oxygen composition which has excellent adhesion and appearance while suppressing changes in hardness such as heat shrinkage and heat.

[Best Practice for Carrying Out the Invention]

Hereinafter, embodiments of the present invention will be described.

The addition-hardening polyfluorene composition of the present invention contains the following components (A) to (E).

(A) a polyorganosiloxane having at least one alkenyl group bonded to a ruthenium atom in one molecule: 100 parts by mass; (B) a polyorganic having at least two hydrogen atoms bonded to a ruthenium atom in one molecule Hydroquinone: for the total amount of alkenyl groups of the above-mentioned (A) component, the hydrogen atom bonded to the deuterium atom is 0.9 to 3.0 mol; (C) the hydronization reaction Catalyst: amount of catalyst; (D) at least one selected from the group consisting of (D1) and (D2) as an adhesion-imparting agent: 0.01 to 10 parts by mass, (D1) having an epoxy group and an alkoxy group selected from the group consisting of At least one of a group consisting of an alkyl group and at least one selected from the group consisting of a hydrogenated alkyl group and a crosslinkable vinyl group, and (D2) having at least one selected from the group consisting of an epoxy group and an alkoxy group. However, the decane or decane compound having no isocylate ring; and (E) the organic radical represented by the above general formula (3): 0.001 to 0.05 parts by mass.

Hereinafter, each component will be described.

[(A) ingredient]

The component (A) is an alkenyl group-containing polyorganosiloxane having a matrix polymer which is a composition of the present invention together with the component (B) described below.

The component (A) is not particularly limited as long as it is a polyorganosiloxane having at least one alkenyl group bonded to a ruthenium atom in one molecule.

The structure of the polyorganosiloxane molecule of the component (A) is not particularly limited, and may be any structure of a linear chain, a branched chain, a ring shape, and a mesh shape, or a combination of these. Both the branched structure and the mesh-like structure may be a two-dimensional structure or a three-dimensional structure. In the present specification, in particular, a molecule composed of a branched structure, a molecule composed of a mesh structure, and a molecule composed of a branched structure and a mesh structure are collectively referred to. It is a molecule of "chain-shaped ‧ mesh-like structure".

In addition, the polyorganosiloxane of the component (A) may be one type of a polyorganosiloxane having a molecular structure of one type or a mixture of two or more types, or a polyorganism having two or more types of molecules. A mixture of one or more of each of oxoxanes. When the component (A) is a mixture, the number of the alkenyl groups bonded to the ruthenium atom in one molecule may be one or more as an average of the entire component (A).

As the component (A), a combination of a linear polyorganosiloxane having at least one alkenyl group bonded to a fluorene atom in one molecule and a polyorganosiloxane having a branched ‧ mesh structure It is better. In the present specification, the term "linear polyorganosiloxane" is a polyorganosiloxane containing a plurality of branched chains in a siloxane skeleton.

Although it differs depending on the use, when the matrix polymer is composed only of a linear polyorganosiloxane, the hardness is insufficient. Among the applications requiring hardness, it is particularly preferred to use a polyorganosiloxane having a linear polyorganosiloxane and a branched ‧ mesh structure. Further, only the linear polyorganosiloxane is used as the component (A), and the hardness can be adjusted to a certain extent by combining the (F) vermiculite powder described later. Further, the (F) vermiculite powder may be used in the case where the component (A) is a linear polyorganosiloxane. The component (A) is a linear polyorganosiloxane having a linear content, and the content of the linear polyorganosiloxane is more than 50% by mass based on the total amount of the component (A). meaning.

The polyorganosiloxane (A1) represented by the following general formula (1) is exemplified as the linear polyorganosiloxane.

(R ¹ ₃ SiO _1/2 )(R ¹ ₂ SiO _2/2 ) _n (R ¹ ₃ SiO _1/2 ) (1)

(However, in the formula (1), R ¹ each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group, and at least two of R ¹ are an alkenyl group; The average degree of polymerization is expressed as 50~2,500).

In addition, the polyorganosiloxane (A2) represented by the following average unit formula (2) is exemplified as the polyorganosiloxane.

(R ² ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c (SiO _4/2 ) _d (2)

(However, in the formula (2), R ² each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group, and at least one of R ² is an alkenyl group; a and d are positive numbers , b and c are 0 or a positive number).

(polyorganooxane (A1))

The polyorganooxynonane represented by the above general formula (1) can be well controlled in the synthesis of a polymer having a high degree of polymerization as shown below. The azide skeleton of (A1) is linear. However, a number of branches, for example, may also have a plurality of branches in the molecule.

The average degree of polymerization of polyorganosiloxane (A1) (ie, the number of units of decane), in the general formula (1), the number of terminal groups is added to n, and is represented by n+2. It is within the range of 50~2,500. The average degree of polymerization is preferably from 100 to 1,500. When the average degree of polymerization of the polyorganosiloxane (A1) is within the above range, there is no problem in synthesis (polymerization), and workability is also good.

The viscosity of the polyorganosiloxane (A1) (25 ° C) is preferably from 100 to 150,000 mPa ‧ , particularly preferably in the range of from 200 to 20,000 mPa ‧ s. When the viscosity of the polyorganosiloxane (A1) is within this range, not only the workability of the obtained composition is good, but also the physical properties of the polyoxysulfide cured product obtained from the composition are good.

Further, unless otherwise specified in the specification, the viscosity refers to the viscosity measured by a rotary viscometer at 25 ° C. Further, the conditions such as the number of rotations at the time of measurement can be appropriately adjusted depending on the viscosity of the sample or the measuring device to be used.

The polyorganosiloxane (A1) has two or more alkenyl groups bonded to a ruthenium atom in one molecule. Further, the number of the alkenyl groups is preferably 250 or less, and more preferably 50 or less. When the number of alkenyl groups exceeds 250 per molecule, the cured product becomes weak and does not exhibit sufficient strength. Further, the number of the alkenyl groups herein is the average number per molecule of the polyorganosiloxane (A1).

The R ¹ in the above general formula (1) is independently an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group. In the general formula (1), the number of alkenyl groups (ratio) of R ¹ in the formula (1) can be appropriately adjusted so that the number of alkenyl groups per molecule is within the above range.

When R ¹ is a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group, examples of the R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. An alkyl group; an aryl group such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group such as a benzyl group or a phenethyl group; a chloromethyl group, a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group; a substituted hydrocarbon group such as 3-cyanopropyl or 3-methoxypropyl.

When R ¹ is an alkenyl group, specific examples of the R ¹ include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group. Since the synthesis or operation of the polyorganosiloxane (A1) is easy and the addition reaction proceeds easily, the alkenyl group is preferably a vinyl group. The alkenyl group may also be bonded to any deuterium atom in the molecule, but since it exhibits excellent reactivity, it is preferred that the moiety be a deuterium atom bonded to the end of the molecule. In the general formula (1), the plurality of alkenyl groups may be the same or different, but are preferably the same in terms of ease of synthesis.

R ¹ other than the alkenyl group, the polyorganosiloxane (A1) has a plurality of R ¹ (hereinafter, R ¹ other than an alkenyl group) represented by a monovalent unsubstituted or substituted hydrocarbon group (hereinafter referred to as "R ¹¹ ") (The number of the number of the above alkenes is subtracted from the number of all R ¹ ). In the polyorganosiloxane (A1), a plurality of R ^{11 's} may be the same or different. R ^{11 is} preferably the same in terms of ease of synthesis. However, depending on the physical properties required for the obtained polyoxysulfide cured product, a different base may be introduced into the portion.

It is easy to synthesize or operate the polyorganosiloxane (A1), and excellent heat resistance can be obtained. It is preferable to use a polyorganosiloxane (A1) which is 50% or more of R ¹¹ as a methyl group. All of R ¹¹ is a methyl group.

Further, for the purpose of adjusting the hardness or the modulus of elasticity of the obtained polyoxysulfuric cured product, a part of R ^{11 which} the polyorganosiloxane (A1) has may be used as a phenyl group, and all of the remaining R ^{11 may} be used. A combination of methyl groups. In this case, a part of R ¹ in the unit surrounded by n in the formula (1) is a phenyl group, and a combination of all of R ¹ other than the alkenyl group other than the alkenyl group in the remaining R ¹ is preferably a methyl group.

Further, for the purpose of imparting oil resistance and/or solvent resistance, a part of R ^{11 which} the polyorganosiloxane (A1) has may be used as 3,3,3- in the obtained polyoxysulfide cured product. Trifluoropropyl, and all of the remaining R ¹¹ are taken as a combination of methyl groups. When this case, the formula n (1) is surrounded by a unit of the R ¹ moiety is 3,3,3-trifluoropropyl, R ¹ other than the alkenyl group among the remaining R ¹ are all methyl The combination is preferred.

When the linear polyorganosiloxane is used as the component (A) in the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention, one type may be used or two or more types may be used in combination. Further, the polyorganosiloxane (A1) may be used alone or in combination of two or more.

When two or more kinds of polyorganosiloxanes (A1) are used, the polyorganosiloxane (A1) may be a mixture of two or more kinds of polyorganosiloxanes (A1) having different average polymerization degrees to adjust the mixture. Viscosity. By group When two or more kinds of polyorganosiloxanes having different average polymerization degrees are used, it is easy to adjust the desired viscosity, and the range of the polyorganosiloxane which can be used becomes large.

(polyorganosiloxane (A2))

The polyorganosiloxane (A2) represented by the above average unit formula (2) has a unit of (R ² ₃ SiO _1/2 ) in a ratio of a:b:c:d (hereinafter also referred to as "M" Unit "), (R ² ₂ SiO _2/2 ) units (hereinafter also referred to as "D units"), (R ² SiO _3/2 ) units (hereinafter also referred to as "T units"), and (SiO _{4/ 2} ) A polyorganosiloxane having a branched or reticular structure of a unit (hereinafter also referred to as "Q unit").

As a constitution of each unit of the polyorganosiloxane (A2), a and d are positive numbers, and b and c are 0 or a positive number. That is, the M unit and the Q unit are necessary structural units, and the D unit and the T unit are arbitrary structural units.

Further, the relationship of a, b, c, and d in the averaging unit formula (2) is preferably such that 0 < a / (c + d) < 3 and 0 ≦ b / (c + d) < 2 is satisfied.

The mass average molecular weight of the polyorganosiloxane (A2) as measured by gel permeation chromatography is preferably in the range of 1,000 to 100,000, and more preferably 3,000 to 30,000. When the mass average molecular weight of the polyorganosiloxane (2) is within the above range, there is no problem in work due to remarkably high viscosity of the composition, and the mechanical strength after hardening is also good.

Still, polyorganosiloxane (A2), as long as the oxirane unit The composition is not limited to the properties in the above range, and may be a solid at normal temperature (25 ° C) or a liquid having a high viscosity of, for example, 200 Pa ‧ s or more.

R ² in each of the oxoxane units contained in the polyorganosiloxane (A2) is a monovalent hydrocarbon group or an alkenyl group which is independently substituted or unsubstituted in each unit; and further has a plurality of R in the same unit. ^{At 2} o'clock, a substituted or unsubstituted monovalent hydrocarbon group or alkenyl group is independently represented in the unit. Specific examples of R ² include the substituted or unsubstituted monovalent hydrocarbon group or alkenyl group represented by R ¹ in the above polyorganosiloxane (A1). And, R ² is preferably about like state, and may also be represented by R ¹ include the same as the group.

The polyorganosiloxane (A2) has at least one alkenyl group bonded to a ruthenium atom in one molecule. The polyorganosiloxane (A2) preferably has two or more alkenyl groups bonded to a ruthenium atom in one molecule. Further, the number of the alkenyl groups in the polyorganosiloxane (A2) is preferably 50 or less. The polyorganosiloxane (2) has one or more alkenyl groups in one molecule, and may be any of the above M to T units.

In the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention, when a polyorganosiloxane having a branched ‧ mesh structure is used as the component (A), one type or two types may be used in combination. the above. Further, the polyorganosiloxane (A2) may be used alone or in combination of two or more.

In the addition-hardening polyfluorene composition of the embodiment of the present invention, the component (A) is an alkenyl group-containing polyorganism of a matrix polymer. Oxane. When a linear polyorganosiloxane is used as the component (A) and a polyorganosiloxane having a branched ‧ mesh structure is used, the ratio can be arbitrarily set depending on the application.

For example, when a member comprising an addition-type polyorganosiloxane (A1) and a polyorganosiloxane (A2) is added to a member for an optical semiconductor element, the polyorganosiloxane (A1) is used. The proportion of the polyorganosiloxane (A2) is preferably from 5 to 60 parts by mass, more preferably from 10 to 30 parts by mass, per 100 parts by mass of the polyorganosiloxane (A2). When the ratio of the content of the polyorganosiloxane (A1) to the polyorganosiloxane (A2) is within the above range, the most suitable hardness and sufficient mechanical strength of the cured product can be imparted to the above application.

[(B) ingredients]

The polyorganohydroquinone having at least two hydrogen atoms bonded to a halogen atom in one molecule of the component (B) acts as a crosslinking component which reacts with the component (A). The molecular structure of the component (B) is not particularly limited, and any of a structure such as a linear chain, a branched chain, a ring, and a mesh may be used, or a polyorganohydrohalosiloxane having various structures may be used.

The polyorganohydroquinone of the component (B) has two or more, preferably three or more "hydrogen atoms bonded to a halogen atom" in one molecule (that is, a hydrogenated alkylene group (Si-H group)). . When the polyorganohydrohalosiloxane of the component (B) is linear, these Si-H groups may be located only at either the end and the intermediate portion of the molecular chain, or may be located therebetween. Further, the number of Si-H groups in this is one molecule per molecule of polyorganohydroquinone. The average number.

The average number of ruthenium atoms (average degree of polymerization) in one molecule of the component (B) is preferably from 2 to 1,000, and more preferably from 3 to 100. The viscosity (25 ° C) of the component (B) is preferably 500 mPa ‧ or less, particularly preferably in the range of 10 to 100 mPa ‧ s. When the viscosity of the component (B) is within this range, not only the workability of the obtained composition is good, but also the physical properties of the polycarbonate cured product obtained from the composition are good.

The polyorganohydrohalosiloxane of the component (B) is preferably used in an amount of from 0.3 to 15 mmol/g, more preferably from 1 to 10 mmol/g, as the Si-H group in the molecule.

As the component (B), for example, a polyorganohydrohalosiloxane represented by the following average composition formula (4) can be used.

R ⁴ _p H _q SiO _(4-pq)/2 (4)

(In the formula (4), R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturation; p and q satisfy 0.7≦p≦2.1, 0.001≦q≦1.0, (p+q) ≦3.0 is a positive number).

As the above R ^{4 ,} for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, decyl, fluorene An alkyl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; and a hydrogen atom in the hydrogen group; Examples of a part or all of the atom include a chloromethyl group, a 3-chloropropyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group and the like. R ^{4 is} preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

Specific examples of the component (B) include methyl hydropolysiloxanes in which both ends of the molecular chain are blocked by a trimethylphosphonyl group, and two ends of the molecular chain terminated by a trimethylphosphonyl group. Methyl decane ‧ methylhydroquinoxane copolymer, dimethyl oxoxane ‧ methylhydroquinone ‧ diphenyl fluorene copolymer copolymerized at both ends of the molecular chain by trimethyl decyloxyalkyl a dimethylpolyoxane terminated by a dimethylhydrogen oxane at both ends of the molecule and the molecular chain, and a dimethylpolyoxane ‧methyl group terminated at the two ends of the molecular chain by a dimethylhydrogen oxane a hydroquinone copolymer, a dimethyl oxane ‧ diphenyl decane copolymer terminated at both ends of the molecular chain by a dimethyl hydroxy siloxane, and a dimethyl hydrogen-containing oxime at both ends of the molecular chain Alkyl-terminated diphenyl polyoxane, a unit of R ⁴ ₃ SiO _1/2 (R ^{4 is} as described above, the same R ⁴ is also the same), R ⁴ ₂ HSiO _1/2 unit, and SiO _4/ a polyorganosiloxane copolymer composed of ₂ units, a polyorganosiloxane copolymer composed of R ⁴ ₂ HSiO _1/2 units and SiO _4/2 units, and a unit of R ⁴ HSiO _2/2 R ⁴ SiO _3/2 units Silicon alumoxane polyorganosiloxane copolymer consisting of HSiO _3/2 units polyorganohydrogen silicon oxide. These may be used alone or in combination of two or more.

As the component (B), among the above polyorganohydroquinones, polymethylhydroquinone (especially, the organic group bonded to the ruthenium atom has only a methyl group) is preferable, and specifically words, R in the average composition formula (4) all ⁴ of the polymethyl hydrogen methyl silicon oxide.

In the addition-curable polyfluorene oxide composition according to the embodiment of the present invention, the content of the polyorganohydrohalosiloxane of the component (B) and the total amount of the alkenyl group (for example, vinyl) of the component (A) 1 mole The Si-H group of the component (B) is in an amount of 0.9 to 3.0 moles. The content of the component (B) is an effective amount of the component (B) of the component (A), and the total amount of the alkenyl group of the component (A) is 1 mol, and the component (B) The amount of Si-H groups is preferably from 1.0 to 2.8 moles, and more preferably from 1.1 to 2.5 moles. When the component (B) is contained in the above-mentioned content, the hardening reaction of the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention is sufficiently performed, and a large amount remains in the polyoxysulfide cured product. Since the unreacted Si-H group is present, the physical properties of the obtained polyoxysulfuric cured product hardly change with time.

[(C) ingredient]

The hydrogenation sulfonation reaction catalyst of the component (C) is a catalyst for promoting an addition reaction (hydrogenation reaction) of an alkenyl group contained in the component (A) and a Si-H group in the component (B). Examples of the component (C) include a platinum-based catalyst, a palladium-based catalyst, and a ruthenium-based catalyst. However, a platinum-based catalyst is preferred from the viewpoint of economy. As the platinum-based catalyst, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and an olefin, a coordination compound of a vinyl siloxane or an acetylene compound, or the like can be used. These may be used alone or in combination of two or more.

The content of the component (C) is not particularly limited as long as it is an effective amount as a catalyst for the hydrogenation reaction, and for example, the total amount (mass) of the component (A) and the component (B) can be set. The conversion to platinum atom is 0.1 to 100 ppm, preferably 1 to 20 ppm, more preferably 1 to 10 ppm. If the content is within this range, it can be fully promoted The addition reaction results in sufficient hardening and is economically advantageous.

In the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention, a predetermined amount of the (A) component and the (B) component polyorganosiloxane and the catalyst amount (C) hydrogenated decane are used. When the catalytic reaction catalyst is used in combination, a polyfluorene cured product having high transparency as a cured product can be obtained.

[(D) ingredient]

The addition-curable polyfluorene-oxygen composition of the embodiment of the present invention contains at least one selected from the group consisting of the following (D1) and (D2), and (D1) having an epoxy group selected from the group consisting of the following (D) and (D2). At least one of a group and an alkoxyalkyl group, and at least one isocyanuric acid derivative selected from the group consisting of a hydrogenated alkyl group and a crosslinkable vinyl group; (D2) having an epoxy group and an alkoxy group selected from the group consisting of At least one of them, but does not have a decane or a decane compound of an isocyanocyanate ring.

The content of the (D) adhesiveness imparting agent in the addition-curable polyfluorene composition is 0.01 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the component (A). In the above-mentioned (D) adhesiveness-imparting agent, in particular, the obtained polyoxysulfuric acid hardener contributes to the plastic, specifically, the adhesion of PPA (polyphthalamide) or the like. .

((D1) component)

The at least one selected from the group consisting of an epoxy group and an alkoxyalkyl group as the component (D1) and at least one selected from the group consisting of a hydrogenated alkyl group and a crosslinkable vinyl group are preferably an isocyanuric acid derivative. Expressed by the following formula (D11) Compound. Hereinafter, the compound represented by the formula (D11) is also referred to as a compound (D11). Further, the compounds represented by other formulae are also the same.

In the formula (D11), Y ¹ to Y ³ are each independently a vinyl group, a methacryloxy group, an acryloxy group, a group represented by the following formula (T1), an alkoxyalkyl group, or an epoxy group. 1 or 2 of Y ¹ to Y ³ is a vinyl group, a methacryloxy group, an acryloxy group or a group represented by the following formula (T1), and the remainder is an alkoxyalkyl group or an epoxy group.

The alkoxyalkylene group may be any of alkoxydialkylalkyl groups in which one alkoxy group and one monovalent hydrocarbon group are bonded to a halogen atom; one alkoxy group and one monovalent hydrocarbon group; a dialkoxyalkyl fluorenyl group bonded to a ruthenium atom; and a dialkoxy fluorenyl group in which three alkoxy groups are bonded to a ruthenium atom. A dialkoxyalkyl fluorenyl group or a trialkoxy fluorenyl group is preferred.

The alkoxy group of the alkoxyalkylene group may, for example, be an alkoxy group having a branched structure having a carbon number of 1 to 4, preferably a methoxy group, an ethoxy group or a propoxy group, and a methoxy group. The base and ethoxy group are particularly preferred. Examples of the hydrocarbon group include a hydrocarbon group which may have a branched structure of 1 to 4 carbon atoms, and a methyl group and a The base and the propyl group are preferred, and the methyl group and the ethyl group are particularly preferred.

Specific examples of the alkoxyalkyl group include a dimethoxymethyl fluorenyl group, a diethoxymethyl fluorenyl group, a trimethoxy decyl group, and a triethoxy fluorenyl group.

Each of Q ¹ to Q ³ is a hydrocarbon group having a valence of 1 to 7 carbon atoms of a linking group represented by the following formula (L1) and an etheric oxygen atom, independently of a carbon-carbon atom. When Q ¹ to Q ³ have a linking group of the following formula (L1), the carbon number does not include the number of carbon atoms of the linking group.

In the formula (T1), s is 1 to 10, and preferably 1 to 4. In the formula (L1), t is 1 to 10, and preferably 1 to 4.

It is preferable that -Q ¹ -Y ¹ , -Q ² -Y ² and -Q ³ -Y ^{3 in} (D11) are each independently a group represented by the following.

-(CH ₂ ) _n1 -vinyl group (however, n1 is an integer of 1 to 4, preferably 1)

-(CH ₂ ) _n2 - epoxy group (however, n2 is an integer of 1 to 4, preferably 1)

-(CH ₂ ) _{n3 -alkoxyalkylene} (however, n3 is an integer of 1 to 5, preferably 3)

-(CH ₂ ) _n4 -(T1) (however, n4 is an integer of 1 to 5, preferably 3)

-(CH ₂ ) _n5 -(L1)-(CH ₂ ) _{n6 -epoxypropoxy} (however, n5 and n6 are integers of 1 to 5, preferably 3)

-(CH ₂ ) _n7 -(L1)-(CH ₂ ) _{n8 -alkoxyalkylene} (however, n7, n8 are integers from 1 to 5, n7 is preferably 3, and n8 is preferably 2)

Specific examples of the compound represented by the formula (D11) include compounds represented by the following formulas (D11-1) to (D11-7).

The component (D1) may be used alone or in combination of two or more. For example, in the compound (D11), the compound (D11-1) and the compound (D11-2), the compound (D11-4) and the compound (D11-5), the compound (D11-6) and the compound (D11-7) are used. Combinations are preferred, with mixtures of molar ratios of 1:1 being particularly preferred.

((D2) component)

As having at least one selected from the group consisting of an epoxy group and an alkoxy group, but having no The component (D2) of the isodecane cyanide or a decane compound is preferably a compound selected from the group consisting of the following formula (D21), a compound represented by the formula (D22), and a formula (D23). At least one of the compounds indicated.

In the formula (D21), in the formula (D22), Y ⁴ , Y ⁵ and Y ⁶ each independently represent an epoxy group, a cyclic alkyl group containing an epoxy group, or an alkoxyalkyl group; Q ⁴ , Q ⁵ , Q ⁶ independently represents a hydrocarbon group having an etheric oxygen atom and an ester-bonded carbon number of 1 to 10 between carbon-carbon atoms; u is represented by 3 to 5; x1 and x2 are independently represented by 1 to 10; R ¹⁰ each independently represents an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydrogen atom or a chlorine atom. However, in the formula (D21), when the Si-H group is present in the formula (D22), R ¹⁰ is a group other than the alkenyl group.

(Y ⁷ -Q ⁷ -) _v -SiR ¹¹ _w X _(4-vw) (D23)

In the formula (D23), Y ⁷ represents an epoxy group or a cyclic alkyl group containing an epoxy group; and Q ⁷ represents a carbon number of 1 to 10 which may have an etheric oxygen atom between carbon-carbon atoms. Hydrocarbyl; v is 1 or 2; w is 0 or 1. X represents a hydrolyzable group selected from an alkoxy group and a chlorine atom; R ¹¹ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a chlorine atom; and if X and (Y ⁷ -Q ⁷ -) are plural, These may or may not be the same.

In the above formula (D21) to (D23), examples of the cyclic alkyl group containing an epoxy group represented by Y ⁴ to Y ⁷ include a 3,4-epoxycyclohexyl group. In the formulae (D21) and (D22), as alkoxyalkylene group represented by Y ⁴ to Y ⁶ and -SiR ¹¹ _w X _{(4-vw) in the case} where X is an alkoxy group in (D23), The alkoxyalkylene group exemplified when the Y ¹ to Y ³ in the above (D11) is an alkoxyalkyl group is the same.

Preferably, -Q ⁴ -Y ⁴ , -Q ⁵ -Y ⁵ , and -Q ⁶ -Y ^{6 in} (D21) and (D22) are each independently represented by the following (i) to (iv). Either.

(i)-(CH ₂ CHCH ₃ -C(=O)-O-) _n11 -(CH ₂ ) _{n12 -alkoxyalkylene} (however, n11 is 1 or 0; n12 is an integer from 1 to 5; Good for 2 or 3)

(ii) -(CH ₂ ) _n13 - epoxy group (however, n13 is an integer of 1 to 5, preferably 3)

(iii) -(CH ₂ ) _{n14 -epoxypropoxy} (however, n14 is an integer of 1 to 5, preferably 3)

(iv) -(CH ₂ ) _n15 -(3,4-epoxycyclohexyl) (however, n15 is an integer of 1 to 5, preferably 2)

Specific examples of the compound represented by the formula (D21) include compounds represented by the following formula (D21-1).

In addition, specific examples of the compound represented by the above formula (D23) include compounds represented by the following formula (D23-1).

The component (D2) may be used alone or in combination of two or more. From the viewpoint of maintaining high adhesion and excellent appearance, at least one of the compound (D21) and at least one compound (D23) are preferred.

In the addition-curable polyfluorene composition of the embodiment of the present invention, (D) the adhesion-imparting agent may be used alone or in combination of two or more. A preferred combination is at least one of the above (D1) isomeric cyanuric acid derivative and at least one of the above (D2) decane or a decane compound. The content ratio of at least one of the above (D1) isomeric cyanuric acid derivative and at least one of the above (D2) decane or a decane compound is a mass ratio represented by (D1)/(D2). Preferably 0.1 to 3.0, and Good is 0.25~1.5. The addition-hardening polyfluorene composition is characterized in that the (D1) component and the (D2) component are contained in such a ratio, and the obtained polyoxysulfide cured product has particularly high adhesiveness, for example, in addition to adhesion. In addition to the improvement, it can also correspond to various adhesives and the like, and can give an excellent appearance.

When the compound having a hydrogenated alkylene group or a crosslinkable vinyl group is used as the component (D), the ratio of the hydrogenated decyl group to the alkenyl group of the entire addition-hardening polyfluorene-oxygen composition is obtained (that is, The (A) component, the component (B), and the ratio of the total amount of the alkylene group in the component (D) to the total amount of the alkenyl group), for example, 1 mol of the alkenyl group, preferably hydrogenated The decyl group is adjusted to be 0.9 to 3.0 moles. The ratio is preferably from 1.0 to 2.8 moles, and more preferably from 1.1 to 2.5 moles.

[(E) component]

The component (E) is an organic radical represented by the following general formula (3). The compound (3) is a nitrogen-containing heterocyclic skeleton having a nitrogen atom number of 5 or 6 members, and the nitrogen is an organic radical bonded to an oxy radical as a nitrogen bonded to the heterocyclic ring. An atom or a group of atoms that are opposite carbon atoms, having at least one electron attracting atom or group.

In the formula (3), R ⁵ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; and R ⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxyl group or a hydroxyl group, or is bonded to the same carbon. Two R ⁶ atoms represent =0, but at least one of R ⁶ is a carboxyl group or a hydroxyl group, or formula (3) has at least one R ⁶ bonded to the same carbon atom to represent =0. .

In the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention, the compound (3) containing the organic radical of the component (E) can suppress the result of the adhesion-imparting agent derived from the component (D). The shrinkage or hardness change of the polyoxygenated hardened material.

Specific examples of the compound (3) include an organic radical of a nitrogen-containing heterocyclic skeleton of five members represented by the following formula (31), and a nitrogen-containing heterocyclic skeleton of six members represented by the following formula (32). Organic free radicals. R ⁵ and R ⁶ in the formula (31) and the formula (32) have the same meanings as R ⁵ and R ⁶ in the formula (3).

The atom or group of R ^{5 in} the formula (31) or the formula (32) is bonded to a carbon atom adjacent to the nitrogen atom of the hetero ring, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. R ^{5 is} preferably independently a linear hydrocarbon group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group, a propyl group; and preferably a linear alkyl group having 1 or 2 carbon atoms, that is, a methyl group or an ethyl group. . The four R ^{5 's} may be the same or different.

The atom or group of R ^{6 in} the formula (31) or the formula (32) is bonded to a carbon atom which is opposite to the nitrogen atom of the hetero ring (specifically, a carbon atom adjacent to the nitrogen atom) On the carbon atom). R ⁶ independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxyl group or a hydroxyl group, or 2 R ⁶ bonded to the same carbon atom to represent =0. At least one of R ⁶ of the formula (3) is a carboxyl group or a hydroxyl group, or at least one of the formulas (3) having two R ⁶ bonded to the same carbon atom represents =0. Hereinafter, a carboxyl group, a hydroxyl group, and =0 are collectively referred to as a substituent (I).

The number of the substituents (I) in the formula (3) is preferably from 1 to 3, more preferably from 1 or 2, most preferably one. Further, in the formula (32), it is preferred that the nitrogen atom at the 1 position has a substituent (I) at a carbon atom at the 4 position. The substituent (I) is an electron attracting group or atom, and has a substituent at a position opposite to the nitrogen atom of the hetero ring. (I), the change in shrinkage or hardness of the obtained polyoxysulfide cured product can be suppressed.

R ⁶ other than the substituent (I) is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. R ⁶ other than the substituent (I) is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom. Specific examples of the compound (3) which can be exemplified as the compound (31) represented by the following formula (31-1), and the compound (32) are classified into the following formulas (32-1) and (32-). 2), or a compound represented by (32-3). In the formulae (31-1) and (32-1) to (32-3), when R ⁶ is a hydrogen atom, the description of "H" is omitted.

Compound (3) can be produced by a known method. Further, in the present invention, a commercially available product can also be used as the compound (3). In the addition-hardening polyfluorene composition of the embodiment of the present invention, the compound of the component (E) (3) One type may be used alone or two or more types may be used in combination. In the addition-hardening type polyoxo composition of the embodiment, the content of the compound (3) of the component (E) is 0.001 to 0.05 parts by mass based on 100 parts by mass of the component (A). It is preferably 0.002 to 0.03 parts by mass. When the ratio of the content of the component (E) of the component (A) is within the above range, the obtained polyoxysulfide cured product can maintain the appearance well and suppress the shrinkage of heat caused by the component (D). And changes in hardness. Further, the obtained polyoxysulfide cured product can sufficiently exhibit the action of the component (D) to maintain excellent adhesion.

[arbitrary component - (F) component]

The addition-hardening polyfluorene composition of the embodiment of the present invention may contain the vermiculite powder of the component (F) as an optional component. The vermiculite powder of the component (F) may be a well-known type which is usually formulated in a polyoxyl cured product. The component (F) has a moderate fluidity and thixotropy to the composition before crosslinking, and a crosslinked body of a polyorganosiloxane obtained by crosslinking, imparting high mechanical properties required for the intended use. The role of strength. In particular, the component (A) is a linear polyorganosiloxane, and for example, when it is composed only of polyorganosiloxane (A1), a vermiculite powder containing the component (F) is preferred.

In order to exhibit the above functions, the vermiculite powder of the component (F) preferably has a specific surface area (hereinafter referred to as BET specific surface area) of BET method of 50 m ² /g or more, and preferably 50 to 600 m ² /g. , 100~400m ² /g is especially good. The type of the vermiculite is not particularly limited, but it may be suitable for use of precipitated vermiculite, smoky vermiculite (pyrolysis vermiculite), and calcined vermiculite. For the point of reinforcement and thixotropy, it is preferable to use a smoky vermiculite.

On the surface of such a vermiculite powder, a large number of stanol groups (Si-OH groups) exist. Accordingly, when the vermiculite powder is directly added to the composition, problems such as thickening and significant plastic recovery are likely to occur. Therefore, it is preferred to hydrophobize the surface of the vermiculite powder. The surface treatment amount is preferably such that the amount of carbon on the surface of the vermiculite is 2.0% by mass or more, and more preferably 3.0% by mass or more. If it is less than 2.0% by mass, the effect of increasing the viscosity and the operable period of the composition is less. In addition, the upper limit of the amount of carbon is not particularly limited, but is generally 20% by mass or less, preferably 12% by mass or less, and particularly preferably 8% by mass or less. The vermiculite powder as the component (F) may be subjected to surface treatment in the form of a powder in advance, or may be subjected to surface treatment in a kneading process.

As the surface treatment method of the vermiculite powder, a generally known surface treatment technique can be employed. Examples of the organic ruthenium compound used as the surface treatment agent include an organic sulfonium alkane, a decane coupling agent, a dimethyl polyoxyalkylene (including a cyclic structure), an organic hydrogen polyoxyalkylene, and the like. Part of the hydrolysis of the reactants.

Examples of the organic sulfonium alkane include 1,3-divinyltetramethyldiazane, 1,3-dimethyltetravinyldiazide, hexamethyldioxane, and the like. Six organic diazane alkane; octamethyl triazane alkane; octahydrotriazane such as 1,5-divinylhexamethyltriazane or the like.

Examples of the above decane coupling agent include methyltrimethoxydecane, ethyltrimethoxydecane, propyltrimethoxydecane, and butyl. An alkyltrialkoxy decane such as trimethoxy decane, dimethyl dimethoxy decane, diethyl dimethoxy decane, dimethyl diethoxy decane, diethyl diethoxy decane, etc. Dialkyl dialkoxy decane; vinyl triethoxy decane, vinyl trimethoxy decane, vinyl methoxy methoxy decane, etc. alkenyl trialkoxy decane, divinyl a dialkyl dialkoxy decane such as dimethoxy decane or divinyl diethoxy decane; a trialkyl alkoxy decane such as trimethyl methoxy decane or triethyl methoxy decane; a trialkenyl alkoxy decane such as trivinyl methoxy decane or trivinyl ethoxy decane; trimethyl chlorodecane, dimethyl dichloro decane, methyl trichloro decane, vinyl trichloro decane, An organochlorodecane such as divinyldichloromethane or trivinylchlorosilane; and chloropropyltrimethoxydecane.

Further, among these, a substituent in which a substituent of a halogen atom other than a hydrolyzable group is a methyl group is a decane coupling agent, a cyclic dimethyl polysiloxane, and an organic decane.

A commercially available product can be used as the vermiculite powder of the component (F). As a commercial item, for example, aerosil 200 (trade name, manufactured by EVONIC, BET specific surface area: 200 m ² /g), aerosil 300 (trade name, manufactured by EVONIC, BET specific surface area: 300m ² /g) and so on. Further, in the present invention, a vermiculite powder obtained by subjecting such a commercially available product to a surface treatment using octamethylcyclotetraoxane or hexamethyldioxane such as a cyclic dimethyl polyoxyalkylene is used. good. The component (F) may be used alone or in combination of two or more.

The content of the component (F) in the composition of the present invention can be appropriately controlled for the viscosity of the composition, and for the component (A) In the case of 100 parts by mass, it is preferably 10 parts by mass or less. As described above, when the component (A) is composed only of polyorganosiloxane (A1), it is preferred to contain the component (F), and the content is 0.1 for 100 parts by mass of the component (A). It is preferably 10 parts by mass, and more preferably 1 to 4 parts by mass. When the content of the vermiculite powder of the component (F) is within the above range, the viscosity of the composition is moderate and the workability at the time of molding can be maintained satisfactorily, and the obtained polyoxysulfide cured product can be sufficiently retained. Characteristics such as mechanical strength or hardness.

[arbitrary component - (G) component]

The addition-curable polyfluorene-oxygen composition of the embodiment of the present invention may contain an addition reaction inhibitor as the component (G) as an optional component. The addition reaction inhibitor of the component (G) does not reduce the catalytic activity of the hydrogenation sulfonation reaction catalyst of the component (C) during storage, and has an inhibitor of the alkenyl group of the component (A) and the component (B). The addition reaction of the -H group and the function of preserving stability of the addition-hardening polyfluorene composition.

As the (G) addition reaction inhibitor, a known type can be used. For example, 1-ethynylcyclohexane-1-ol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl Acetylene-based alcohol such as -1-penten-3-ol, phenylbutynol, etc.; 3-methyl-3-penten-1-ene, 3,5-dimethyl-1-hexyne-3 - an acetylene compound such as an alkene; a reaction product of such an acetylene compound with an alkoxy decane, an alkoxy decane, a hydrooxane or a hydroquinone; a tetramethylvinyl fluorene ring; Vinyl oxoxane; organic nitrogen compounds such as benzotriazole and other organophosphorus compounds; , organic chromium compounds, diallyl maleate, and the like.

The content of the addition reaction inhibitor of the component (G) is not particularly limited as long as it can provide the stability of the addition-curable polyfluorene composition, but it is 100 parts by mass of the component (A). It is preferably 0.001 to 0.1 parts by mass, more preferably 0.01 to 0.05 parts by mass.

[arbitrary component - (H) component]

The addition-curable polyfluorene-oxygen composition of the present embodiment can maintain the appearance while suppressing the change in shrinkage or hardness of heat, and maintaining excellent adhesion. In addition to the component (E), a metal carboxylate (hereinafter also referred to as a metal carboxylate (5)) represented by the following general formula (5) as the component (H) may be further contained: 0.001 to 0.015 parts by mass. The content of the component (H) is preferably 0.002 to 0.010 parts by mass in terms of metal atom, based on 100 parts by mass of the component (A). Further, the addition-hardening polyfluorene oxide composition contains the carboxylic acid metal salt (5) as the component (H), and the obtained polysulfide cured product is used to coat, seal, or the like a metal member (for example, a silver electrode). This will protect against such corrosion.

(R ³ COO) _k M...(5)

(M represents a metal atom selected from the group consisting of Ce, Fe, Cr, La, Nd, Pr, Sm; k represents a positive number of 2 to 4; and R ³ represents a substituted or unsubstituted hydrocarbon group having 4 to 17 carbon atoms).

In the general formula (5), M represents a metal atom selected from the group consisting of Ce, Fe, Cr, La, Nd, Pr, and Sm. The M system may be selected from one of the above-mentioned Ce, Fe, Cr, La, Nd, Pr, and Sm, or may be composed of a mixture of two or more kinds. Specific examples of the mixture include a mixture of rare earth elements of Ce, La, Nd, Pr, and Sm, and a mixture of cerium (Ce) as a main component is preferred. Further, the mixture containing ruthenium as a main component means a mixture in which the content of ruthenium exceeds 50% by mass based on the total amount of the mixture.

As the carboxylic acid metal salt (5) used in the component (H), it is preferred that M in the formula (5) is a carboxylic acid metal salt of cerium (Ce) alone, iron (Fe) alone or chromium (Cr) alone. Particularly preferred is a metal salt of a carboxylic acid which is a separate oxime. k is based on the price of the metal used, which can be 2~4.

R ³ is a substituted or unsubstituted carbon number 4 to 17 one-valent hydrocarbon group of the same kind or different kinds, and as a carboxylic acid which provides such a metal salt of a carboxylic acid, for example, 2-ethylhexanoic acid, octanoic acid, Tannic acid, oleic acid, lauric acid, stearic acid, and the like. Further, it may be a mixture of carboxylic acids such as naphthenic acid.

Specific examples of the metal carboxylate (5) include ruthenium (III) octoate, ruthenium (III) 2-ethylhexanoate, iron (II) 2-ethylhexanoate, and 2-ethylhexylate. Iron (III) acid, chromium (III) 2-ethylhexanoate, cerium (IV) citrate, cerium (III) citrate, etc., with cerium (III) octoate and cerium 2-ethylhexanoate (UI) Very good. Further, an octoate or 2-ethylhexanoate salt of a rare earth element mixture containing ruthenium as a main component can also be preferably used. When a mixture of rare earth elements containing cerium as a main component is used, it is advantageous in terms of economy. The higher the content of rhodium in the mixture (ie, the higher the purity of rhodium), It is preferred in terms of effects.

Commercially available products can also be used as the component (H). For example, rare earth-OCTOATE 6% (trade name, DIC company, 2-ethylhexanoic acid rare earth element salt (rare earth element content: 6% by mass, Ce: 3.1% by mass; Nd: 0.95 mass%; Pr: 0.31 mass%; Sm: 0.01 mass%; La: 1.59 mass%), NIKKA OCTHIX Fe (trade name, manufactured by Nippon Chemical Industry Co., Ltd., iron (III) 2-ethylhexanoate (metal) Content: Fe: 6 mass%)), 8% chromium Hex-Cem (trade name, OMG Americas Inc., 2-ethylhexanoic acid chromium (III) (metal content: Cr: 8 mass%)), etc. .

Further, a metal carboxylate (5) such as cerium (III) octoate, cerium (III) 2-ethylhexanoate, a rare earth element salt of 2-ethylhexanoic acid, iron (II) 2-ethylhexanoate, (III), chromium (III) 2-ethylhexanoate or the like is preferably used as an organic solvent solution from the viewpoint of easiness of handling or compatibility with other components in the composition. As such an organic solvent, for example, a petroleum solvent such as a standard solvent, mineral spirits, gas oil or petroleum ether, or an aromatic solvent such as toluene or xylene may be mentioned.

[Other optional ingredients]

The addition-curable polyfluorene-oxygen composition of the embodiment of the present invention contains the components (A) to (E) as essential components in the above-mentioned content, and these are required to be contained in the above-mentioned requirements. The component (F), the component (G), and the component (H) are contained in an amount as an optional component.

The addition-curable polyfluorene composition of the present embodiment is In the range which does not impair the effect of the present invention, any component other than the components (F) to (H) may be further added: polyorganosiloxane, pulverized vermiculite (quartz fine powder), alumina, or the like other than the above. A conductive filler such as an inorganic filler or a silver powder other than the vermiculite powder of the component (F), for example, a phosphor for obtaining a desired luminescent color when used in an optical semiconductor device, toluene, xylene, hexane, An organic solvent such as heptane, ethanol, isopropyl alcohol, acetone or methyl ethyl ketone, a dye, a pigment, a flame retardancy imparting agent, a heat resistance improving agent, an oxidation resistant deterioration agent, a wavelength adjusting agent, and the like.

In the method for producing the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention, the order of addition of each component is not particularly limited, and the necessary components of (A) to (E) are kneaded by a well-known kneader. And a method of the (F) component, the (G) component, the (H) component, and the other arbitrary components which are optional components which can be preferably added.

When the metal carboxylate (5) as the component (H) is used in the form of an organic solvent solution, the component (A) and the organic solvent solution of the metal carboxylate (5) may be mixed in advance. The operation of removing the organic solvent from the mixture is carried out. In this case, the residual component is added to the mixture after the organic solvent removal and kneaded. Further, even when the carboxylic acid metal salt (5) of the component (H) is used as an organic solvent solution, depending on the amount of the organic solvent, an addition hardening type polyoxane composition constituting the component (H) may be used. All the components of the material are mixed by a kneading machine at the same time.

According to the need, the kneading machine is provided with a heating method and a cooling method, and examples thereof include a planetary mixer, a three-roll mixer, and a kneading machine. Machines, Shinagawa mixers, etc. can be used alone or in combination.

The hardening of the addition-curable polyfluorene-oxygen composition of the embodiment of the present invention is mainly carried out by hydrogenation of the component (A) and the component (B) in the presence of the component (C). At this time, the hardening reaction can be appropriately adjusted depending on the kind of the above-mentioned addition reaction inhibitor or the amount of addition. Examples of preferable curing conditions include heating at 50 to 200 ° C for 60 to 300 minutes. The polyoxygenated hardened material obtained in this manner has a hard rubbery or flexible resinous shape, and has excellent adhesion and appearance, and at the same time, can suppress changes in heat shrinkage and heat hardness.

The addition-hardening polyfluorene composition of the present invention is used when an optical semiconductor wafer such as an LED is mounted on a substrate and sealed, for example, as a sealing agent or a die attaching agent for COB (direct wafer packaging). Excellent. Moreover, it can be widely used in a general-purpose optical semiconductor package such as a photodiode, a CCD, or a CMOS.

In the optical semiconductor device in which the optical semiconductor wafer is sealed, the additive structure to which the optical semiconductor wafer is mounted is not particularly limited, for example, a sealing agent or a die attaching agent of the present invention is used as a sealing agent or a die attaching agent. It can be packaged, and can also be a packageless support substrate, such as ceramic substrate, germanium substrate, glass epoxy substrate, phenolic plastic (epoxy) substrate, metal substrate, plastic (specifically PPA (poly O-phthalamide resin) substrate, etc.). Further, when the addition-curable polyfluorene-oxygen composition of the present invention is used, in particular, for a PPA substrate, a highly adhesive polysulfonated cured product can be obtained. Further, in response to regulations The polyoxygenated hardened material obtained by the lattice can also be used as an addition-curable polyfluorene-oxygen composition excellent in adhesion to metals. Further, it is also possible to form an addition-curable polyfluorene-oxygen composition which is excellent in adhesion between a polycarbonate hardened material obtained by a specification and a metal (for example, silver).

[Examples]

The following are examples of the invention, but the invention is not limited to the examples. Further, in the following examples, the viscosity is a measured value at 25 °C.

In the following examples and comparative examples, the following compounds and the like were used as the components (A) to (H). In the following description, Vi is a vinyl group and Me is a methyl group, respectively.

(A) component: polyorganosiloxane (A1), polyorganosiloxane (A2) (polyorganosiloxane (A1): linear methylvinyl polyoxyalkylene (A11))

It is represented by the average composition formula (ViMe ₂ SiO _1/2 ) (Me ₂ SiO _2/2 ) _m1 (ViMeSiO _2/2 ) _m2 (ViMe ₂ SiO _1/2 ), and the average degree of polymerization is 450 (m1 = 448, m2). =0), a linear methylvinyl polyoxyalkylene (A11) having a viscosity of 5000 mPa·s and an average of two vinyl groups per molecule.

(polyorganosiloxane (A1): linear methyl vinyl polyoxyalkylene (A12))

It is represented by the average composition formula (ViMe ₂ SiO _1/2 ) (Me ₂ SiO _2/2 ) _m3 (ViMeSiO _2/2 ) _m4 (ViMe ₂ SiO _1/2 ), and the average degree of polymerization is 89 (m3 = 75, m4). = 12), a linear methyl vinyl polyoxyalkylene (A12) having a viscosity of 200 mPa ‧ and an average of 12 vinyl groups per molecule.

(polyorganosiloxane (A2): branched ‧ mesh methyl vinyl polyoxyalkylene (A21))

It is composed of Me ₃ SiO _1/2 unit, ViMeSiO _2/2 unit, and SiO _4/2 unit, and has a mass average molecular weight of 12,000, and an average of 12 vinyl groups per molecule. Vinyl polyoxane (A21).

(B) Component: linear methyl hydrogen polyoxyalkylene (B1)

It is represented by the average composition formula (Me ₃ SiO _1/2 )(HMeSiO _2/2 ) _m5 (Me ₂ SiO _2/2 ) _m6 (Me ₃ SiO _1/2 ), and the average degree of polymerization is 41 (m5=23, m6). =16), the viscosity is 20 mPa‧s, and the average amount of Si-H per molecule is 24 (8.8 mmol/g) of linear methylhydropolysiloxane (B1).

(C) component: hydrogenation oximation reaction catalyst

A complex of chloroplatinic acid with divinyltetramethyldioxane (sometimes referred to simply as "platinum catalyst").

(D) component: adhesion imparting agent (D1), adhesion imparting agent (D2)

The above compounds (D11-1) and (D11-2) were used as the adhesion imparting agent (D1). Specifically, a mixture of (D11-1) and (D11-2) of 1:1 (mole ratio) was used.

The above compounds (D21-1) and (D23-1) were used as the tackifier (D2).

(E) component: an organic radical represented by the above formula (3)

Compound (31-1): 3-carboxy-PROXYL (manufactured by Tokyo Chemical Industry Co., Ltd., product number: C1406)

Compound (32-1): 4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., product number: H0865)

Compound (32-2): 4-sided oxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., product number: O0266)

Compound (32-3): 4-carboxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., product number: C1428)

(E)' component: a structurally similar organic radical other than the compound (3) used in the comparative example

A compound represented by the following formula (3cf-1) (TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., product number: T1560)), a compound represented by the following formula (3cf-2) (4-amino-TEMPO (Tokyo Chemical Co., Ltd.) Industrial company system, product number: A1343))

(F) component: vermiculite powder

Vermiculite powder (F1): Hexamethyldiazane was used to treat a fumed vermiculite having a specific surface area of about 200 m ² /g. The amount of carbon on the surface of the vermiculite was 2.5% by mass.

(G) component: addition reaction inhibitor

Diallyl maleate (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 97% by mass or more)

(H) component: metal carboxylate (5)

Cerium (III) 2-ethylhexanoate (using 12% hydrazine Hex-Cem (trade name, manufactured by OMG Americas Inc., metal content: Ce: 12% by mass, composition of bismuth 2-ethylhexanoate (III) ): 49% by mass, 2-ethylhexanoic acid: 48% by mass, dipropylene glycol monomethyl ether: 3% by mass)

[Examples 1 to 15 and Comparative Examples 1 to 5]

All the components shown in Tables 1 to 3 were kneaded and degassed, and the addition-curable polyfluorene oxide compositions of Examples 1 to 15 and Comparative Examples 1 to 5 were produced, respectively.

In addition, the content of the component (C) in Tables 1 to 3 is the content (ppm) in terms of platinum atom based on the total mass of the components (A) and (B). In addition, the mass part of the carboxylic acid metal salt (5) of the (H) component is a mass part in terms of a metal atom of the carboxylic acid metal salt (5). In Tables 1 to 3, the total of the Si-H group/(A) component of the component (B), the Vi group (the molar ratio), and the entire composition, that is, the component (A) and the component (B), D) Si-H group/Vi group (Morby ratio) of the component.

<evaluation>

Next, the addition-curable polyfluorene oxide compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 5 were cured by the following method to prepare a polyfluorene cured product test piece, and the obtained test piece was measured by the following method. Initial hardness (TYPE A), quality, and appearance. Next, after the polyfluorene cured product test piece was placed in a high temperature atmosphere, the hardness (TYPE A) and the mass were measured in the same manner, and the hardness (TYPE A) change and the mass change were evaluated. Further, a polyfluorene cured product was formed on the PPA substrate by using the addition-hardening polyfluorene composition obtained in each of the examples by the following method, and the adhesion was evaluated. The results are shown in the lower fields of Tables 1 to 3.

(Production of polyfluorene cured test piece)

At 150 ° C for 60 minutes, the composition obtained above will be The material was hardened to obtain a 60 x 25 x 6 mm block test piece for evaluation. For the obtained test piece, the hardness (TYPE A) and the mass were measured, and the appearance was evaluated.

[hardness]

The hardness (TYPE A) at 25 ° C was measured using a Type A durometer in accordance with JIS K6249 for the obtained test piece of the cured product. Also, the obtained hardness (TYPE A) has an error range of ±1.

[quality]

The mass was measured for the obtained test piece of the cured product using an electronic analysis scale (product name: AEU-210, manufactured by Shimadzu Corporation). The obtained mass has an error range of ±0.001 g, and the mass change rate (%) has an error range of ±0.01%.

[Exterior]

The appearance of the obtained cured test piece was evaluated using the following criteria.

○: Rendered transparently.

△: Only a little turbid.

×: There is turbidity.

(high temperature test)

A polythene oxide hardened test piece after the initial hardness and quality have been measured After being placed in a high temperature atmosphere at 200 ° C for 10 days, the hardness (TYPE A) and the mass were measured in the same manner as above.

[Hardness change, hardness change rate, mass change rate]

The value of the initial hardness (Hi) was subtracted from the hardness (Hh) after the high temperature test as the hardness change. Further, (hardness after initial hardness-high temperature test) / initial hardness × 100 was determined as hardness change rate (%). Further, (the mass after the initial mass-high temperature test) / the initial mass × 100 were determined as the mass change rate (%). Still, the rate of change in mass is an indicator of the contraction of heat, and the smaller the rate of change in mass, the smaller the heat shrinkage.

[Measurement of adhesion to PPA]

The addition-curable polyfluorene oxide composition obtained in each of the above examples was applied to the surface of the substrate made of PPA so as to have a length of 50 mm, a width of 10 mm, and a thickness of 1 mm, and was cured at 150 ° C for 60 minutes. Thereafter, the polysulfonated cured product was scraped off from the surface of the substrate with a metal spatula, and the peeled state of the cured product at this time was investigated. Moreover, the adhesion was evaluated using the following criteria.

○: The cured product could not be peeled off from the interface (surface) of the substrate, and the cured product was destroyed.

△: Part of the cured product was peeled off from the interface (surface) of the substrate, and a part of the cured product was broken.

×: The cured product may be peeled off from the interface (surface) of the substrate.

It can be seen from Tables 1 and 2 that the polyoxysulfuric cured product obtained by curing the addition-curable polyfluorene-oxygen composition of the examples has excellent adhesion and appearance, and is subject to heat shrinkage and hardness change. less. In contrast, the addition-hardening polyfluorene composition of the comparative example shown in Table 3 was hard. The polyfluorene cured product obtained after the chemicalization may have insufficient adhesion, appearance, hardness, and heat shrinkage.

Claims (10)

An addition-hardening polyfluorene-oxygen composition comprising: (A) a polyorganosiloxane having at least one alkenyl group bonded to a ruthenium atom in one molecule: 100 parts by mass; (B) 1 molecule a polyorganohydroquinone having at least two hydrogen atoms bonded to a halogen atom: for the total mole of the alkenyl group of the above component (A), the hydrogen atom bonded to the germanium atom becomes (C) hydrogenation decaneization reaction catalyst: amount of catalyst; (D) at least one selected from the following (D1) and (D2) as an adhesion-imparting agent: 0.01 to 10 (D1) having at least one selected from the group consisting of an epoxy group and an alkoxyalkyl group, and at least one isocyanuric acid derivative selected from the group consisting of a hydrogenated alkyl group and a crosslinkable vinyl group, (D2) a decane or a decane compound having at least one selected from the group consisting of an epoxy group and an alkoxy group but having no heterocyanate ring; and (E) an organic radical represented by the following general formula (3) : 0.001 to 0.05 parts by mass, (In the formula (3), R ⁵ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; and R ⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxyl group or a hydroxyl group, or is bonded to the same Two R ^{6 of} carbon atoms represent =0, but at least one of R ⁶ is a carboxyl group or a hydroxyl group, or formula (3) has at least one of two R ⁶ bonded to the same carbon atom. O). The addition-hardening polysiloxane composition according to claim 1, wherein the component (A) is a polyorganosiloxane (A1) represented by the following general formula (1), and an average unit formula (2) The polyorganosiloxane (A2) represented by (R ¹ ₃ SiO _1/2 )(R ¹ ₂ SiO) _n (R ¹ ₃ SiO _1/2 ) (1) (however, In (1), R ¹ each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group, and at least two of R ¹ are an alkenyl group; an average polymerization represented by n+2 Degree is 50~2,500), (R ² ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c (SiO _4/2 ) _d (2) (however, In the formula (2), R ² each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group which does not contain an aliphatic unsaturated group, and at least one of R ² is an alkenyl group; a and d are positive numbers, b and c is 0 or a positive number). The addition-hardening polyfluorene composition of claim 2, wherein the relationship of a, b, c, and d in the above average unit formula (2) satisfies 0<a/(c+d)<3 and 0≦b/(c+d)<2. The addition-hardening polyfluorene composition of claim 2 or 3, wherein the polyorganoindene is 100 parts by mass of the total of the polyorganosiloxane (A1) and the polyorganosiloxane (A2). The ratio of the oxane (A2) is 5 to 60 parts by mass. The addition-hardening type polyoxane composition of claim 1, wherein the component (A) mainly contains a polyorganosiloxane (A1) represented by the following general formula (1), and further contains (F) Vermiculite powder: 0.1 to 10 parts by mass, (R ¹ ₃ SiO _1/2 )(R ¹ ₂ SiO) _n (R ¹ ₃ SiO _1/2 ) (1) (however, in the formula (1), R ¹ The monovalent unsubstituted or substituted hydrocarbon group independently represents an alkenyl group or an aliphatic unsaturation group, and at least two of R ¹ are alkenyl groups; and the average degree of polymerization represented by n + 2 is 50 to 2,500). The addition-hardening polyfluorene oxide composition according to any one of claims 1 to 5, wherein the (B) polyorganohydroquinone is represented by the following general formula (4), R ⁴ _p H _q SiO _{(4-pq) / 2} (4) (In the formula (4), R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturation; p and q satisfy 0.7≦p≦2.1 , 0.001 ≦ q ≦ 1.0, (p + q) ≦ 3.0 positive number). Addition-hardening polyfluorene composition according to any one of claims 1 to 6 The (D) adhesion imparting agent contains at least one of the above-mentioned (D1) isomeric cyanuric acid derivative in a mass ratio of 0.1 to 3.0 as represented by (D1)/(D2). At least one of the above (D2) decane or a siloxane compound. The addition-hardening polyfluorene composition according to any one of claims 1 to 7, which further comprises (G) an addition reaction inhibitor: 0.001 to 0.1 part by mass. The addition-hardening polyphosphonium composition according to any one of claims 1 to 8, which further comprises (H) a metal carboxylate salt represented by the following general formula (5): 0.001 in terms of metal atom 0.015 parts by mass, (R ³ COO) _k M (5) (M represents a metal atom selected from Ce, Fe, Cr, La, Nd, Pr, Sm; k represents a positive number of 2 to 4; R ³ represents a substitution or Unsubstituted carbon number 4 to 17). The addition-hardening polyfluorene oxide composition according to any one of claims 1 to 9, which is used for sealing an optical semiconductor element or for die bonding.