TWI293082B - - Google Patents

Description

1293082 IX. Description of the Invention: [Technical Field] The present invention relates to a resin composition for an exothermic material, and a heat dissipating material for a crucible, for a hardening material The composition is excellent in heat resistance after heat dissipation, such as hardenability, mm (d), (iv) hardening of the mountain by the m compound, flexibility, and conduction of the heat material. ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, = piece rr, display - integrated circuit = rise:: into::::=r... piece... Infringement of the heat sink is not only the heat conduction type, the type of W pull u, the current 1 good 4, the insertion of the heating element with the metal or the ... It is required to use between the heat sinks, so it is required to: the adhesion of the body or the heat sink _ cup · 7 ^ /, hair... good for the heat transfer area (contact area) to expand or 疋 for the use of parts have good & y witch It is necessary to have good tunneling properties, two plasticity (softness), and further, it is necessary to have these properties (durability) for a long time. For the resin used for the heat dissipating material, it is known that there is a resin containing a hydrolyzable formamyl group (refer to the 曰 々 々 π π 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 6 3 4 2 9 bulletin). However, in the Japanese Patent Laid-Open Publication No. 2001-30293, there are many, for example, compounds having two or more hydrolyzable stones in one molecule, as listed therein. The poly(m-) acrylic acid vinegar in the resin is only exemplified herein, but there is no description about 2226-6964-PF 5 1293082 = of poly(m-) acrylate. In addition, in the patent of the special opening, the patent has the principle of adding water-decomposable base. In the butene, the structure of the main chain is composed of a low-strength bond, and the strength is poor.茫P ^ 'Even if these polymers are hardened to obtain a heat sink, only::: A heat sink with a low degree of heat. If the heat sink strength is weak, insert a film between the heat and the heat body ==, or In the case of a heating element and a dissipative surface, it is possible to use a heat release sheet in the case of r, and it is possible to rupture in the case of the use of, for example, in the Japanese Patent Publication No. 2002-363429. A thermal conductive composition having a hardening property of an adhesive. The so-called (4): 1: is kept in a storage container and is taken out from a storage container: a turbulent atmosphere The 'surface hardening of the composition' becomes rubbery and plastic: the inside of the composition does not harden and remains liquid or gelatinous. 2: Two use tools! Adhesive hardening composition as heat dissipation material month The temperature of the working environment or the change of the gas causes the hardening process = the average of the obtained heat sink The adhesion, flexibility, endurance molybdenum: it "may be reduced. Furthermore, in the special opening 2°°2-363429, the heat-dissipating material which hardens the composition in advance (for example, in the case of a solid which is a solid, it is lacking in adhesion, and is in the range of μ degrees) It is in the form of a sheet, so the thermal conductivity is not good. However, there is no description about the resin composition of the heat sink used for the purpose of obtaining a heat sink for inserting a heat generating body with a metal plate or a heat dissipating blade. 'Consider the above prior art issues to mention

2226-6964-PF ^1293082 For: a heat-dissipating material (such as a heat sink) that is inserted between a heating element and a metal plate or a heat-dissipating blade, which is excellent in adhesion, flexibility, thermal conductivity, and durability, and is formed to A resin composition for a heat dissipating material having excellent heat curable properties as a heat dissipating material is disclosed as a subject. SUMMARY OF THE INVENTION The present invention for solving the above problems is a tree waste composition for a heat dissipating material which is obtained by blending a propylene-based polymer (A) and a thermally conductive filler (8). The propylene-based polymer (1) has a hydrolyzable formyl group and has a glass transition temperature of 1 °C or less. In the above-mentioned (meth) propylene-based polymer (A), the polymer (the ratio of the constituent unit having a hydrolyzable formyl group in the oxime is not included in the above-mentioned resin composition for a heat-dissipating material, but also 15 〇 〇 3 3 3 3 3 3 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Further, the liquid resin containing (A) as an essential component is also contained. Further, in the present invention, a heat dissipating material obtained by curing the resin composition for a heat dissipating material is also included. [Embodiment] The resin composition for a heat dissipating material of the present invention (hereinafter, simply referred to as "resin, port, and material") is a combination of a (meth) acryl-based polymer (A) and a thermally conductive filler (B). The body (1) has an X-knife solution I-alkylene group and the glass transition temperature is below the work temperature.

2226-6964-PF 7 1293082. In the present invention, (8) acryl-based polymerization (four) m into the mass state of '50% of the mass is σ rainbow and 70% by mass or more and 〇Κ σ (between) acrylic vinegar, the above is 佺And better than 8〇% by mass. Further, "acrylic" means "acrylic" and "isobutyl".曰^ as a hydrolyzable progeny, there is no special: limited, as long as at least one hydrolyzable group is bonded to =:, for example, sputum-bonded oxy group, acetate group, time base, ugly amino group, Amino group, gas k group, propylene (tetra) (acetonyl group), halogen atom, hydrogenogen & ^ can be easily adjusted for the usable time of the resin composition (PQt H (8) is preferably used for the sulphur base. It is also possible to introduce a hydrolyzed succulent base into the human body. The method of introducing the hydrolyzable sarcophagus (4) into the propylene-based condensed body (A) is, for example, a polymerizable property in the molecule. Saturated base and force: a single substance (such as r-methylpropenyl propyl methacrylate) and a copolymer of other singly (common) aggregates As a method of 帛i), a single amount (for example, acrylic acid or the like) having a polymerizable unsaturated group and a reactive functional group (hereinafter abbreviated as a hydrazine functional group) in one molecule, and other quantities as necessary The obtained polymer suspension, "and has the ability to add moisture in one molecule:; pit base a compound of a functional group (hereinafter abbreviated as a γ functional group) of an X functional group (for example, a glycidoxypropyltrimethoxydecane having an epoxy group reactive with a carboxyl group in a copolymer) The method of the reaction (as the second method). These methods can be used in combination with two or more methods. 2226-6964-PF 8 1293082 The X functional group and the γ functional group are derived from a carboxyl group or a thiol group. a combination of at least one functional group selected from the group consisting of an amino group, a hydroxyl group, and a hydroxyl group, and a combination of at least one functional group selected from the group consisting of an isocyanate group, an epoxy group, and an anhydrous carboxylic acid group For example, in the case where the X functional group is a carboxyl group, a compound having a hydrolyzable alkylene group and an epoxy group in one molecule is, for example, 2-(3,4-epoxycyclohexyl)B. a trimethoxy decane, a τ-glycidoxypropyltrimethoxy decane, etc. If the X functional group is an isocyanate group, a compound having a hydrolyzable formyl group and an amino group in one molecule is exemplified. Ν-2-(aminoethyl) 3-aminopropyl trimethyl矽, Ν - 2 - (aminoethyl) 3 - aminopropyl decyl decyl oxane, 3 - aminopropyl triethoxy decane, etc. Hydrolyzable formyl group for (m) propylene based polymer The introduction position of (human) is not particularly limited, and may be located at the side chain of the polymer, at the end, or at both the end and the side chain.

The unit of the origin of the constituent unit of the present invention means the one-component monomolecular alkyl group constituting the polymer.

2226-6964-pp 9 1293082 The first method of the first method and the second method can be mentioned. In the case of the propylene-based polymer (1), the hydrolyzable constituent unit occupies κ 解 生 生 矽 而 而 而 而 而 而 而 而 而 而 而 而 而 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The lower limit value is preferably 0.05 mol% or more, and 〇1 mol = er/. The following is the best. 3 Moore ^ best. With the foot...more than Moore's better, the obtained material" limits, lower limit values, and the hardenability of the compound and the usable time are obtained from the spear. The degree of hardening m and the flexibility tend to be high. In the case of the mountain, the composition of the polymer is singularly hydrolyzed by the hydrolyzed methacrylate. The ratio calculation method 'is calculated based on the amount of the polymerizable unsaturated group and the oxime energy group which have been reacted with the hydrolyzable formyl group and the oxime-functional group. The above (meth) propylene-based polymer (4) can be, for example, a monomeric body having a polymerizable unsaturated group and a hydrolyzable formyl group in one molecule, and a well-known (poly) polyacrylate. Copolymerization to get (the third method). Among them, in order to increase the flexibility of the obtained exothermic material, it is preferred to use an alkyl (meth) acrylate having an alkyl group of 2 to 18 carbon atoms. Specific examples thereof include ethyl (meth) acrylate, η-propyl (inter) acrylate, ' i - propyl (inter) acrylate, η - butyl ( meth) acrylate, and butyl butyl Acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-pentyl propyl phthalate, i-pentyl acrylate, octyl Propionate, 2226-6964-PF 10 1293082 1 octyl acrylate, decyl-tetradecyl acrylate, dodecane = (yl) acrylate, thiol (meth) acrylate , 壬 壬 ( 间 间 · · · 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 基 基 基 基 基 基 基 壬 壬 壬 壬 基 基 基 基 基 基 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸 癸Acrylate and the like. When the alkyl group having a carbon number of 2 to 18 is used, the amount of the (meth)acrylic acid alkyl ester is constituting the monomer component of the propylene-based polymer 1 〇β mass%, preferably 50% by mass or more. It is more preferably 7 〇 mass% or more, and the amount % or more is optimal. There are no polymerizable unsaturated groups and hydrolyzable formamidines in the knife, but there is no special duty, but from the above (and) acrylic acid (iv), the (meth) acryl monomer and Ethylene series::... The propylene-based mono-1 body having a hydrolyzed water-soluble base can be exemplified by γ-methyl ketone ^^一*丁平...._ ethenylpropyltrimethoxy decane as a vinyl hydrazine In the case of the first body, it can be cited as "1", "vinyl chlorodecane, acetonitrile dioxane, vinyl tri-field-G emulsion, decyl ethoxy) decane, and the like. Te Zhao

The arrow σ 3 in the instruction manual of 63-1 1 2642, and the early body of the corpse I can also be used. The molecular weight of the (meth) propylene-based polymer (A): the color layer analyzer under the polystyrene conversion of the 'quantity=value:: about right and left, ... _ is better, about two 取" The upper limit is 2 million 80 葸 / 曰 曰 # # 丄 工 工 right, about 1 million is better, L: set the above upper limit, lower limit, the viscosity of the resin composition is low The property is improved, and the right can be p. 'The hardening of the resin composition can be carried out in a short B inch. (5) - The hardening degree of the obtained heat dissipating material is uniform and dense. Sexuality and softness have a tendency to improve.

2226-6964-PF ^293082 The resin composition of the present invention contains a conductive filler (8) (hereinafter, simply referred to as filler 2: heat of thermal conductivity, for example, inorganic filler (aluminum oxide, ruthenium filler) 'Non-nitride, nitriding, nitrogen cutting, hydrating, and secondary: zinc, carbon carbide, etc.), metal fillers (silver, copper, Shaoxu, emulsified stone, their metal alloys, etc.) ), furnace Li 埴 ^, ·, nickel, tin, and anti-system fillers (carbon, stone black 笙, 癸, seeking high electrical insulation when the soil ', ° in the main 丨 丨 巾 糸埴夯 糸埴夯 糸埴夯 糸埴夯 糸埴夯The above-mentioned fillers may be used alone or in combination of two or more kinds. The shape of the filler may be described as a spherical shape, a fibrous shape, a scale shape, an external appearance, an indefinite shape, or the like. 'It is not particularly limited. It is recommended that the filler be excellent in thermal conductivity. For example, the thermal conductivity is used in the test, and the above is the conductivity. The conductivity of the filler is used to sinter the product. ς k, 本/古y由,岩士η〇τ i;lsk method using thermal conductivity measuring device (model TPA-501; Beijing It is measured by the electronics industry. The ratio of the filler in the month of the resin composition is 5% by mass. The lower limit is preferably about 30%, preferably about 4% by mass, and the mass is about 5〇. Preferably, the upper limit is about 95% by mass, preferably about 93% by mass, and about 9% by mass. The ratio of these fillers in the resin composition is the same as that of heat transfer. The performance is increased, but on the other hand, the flexibility of the heat dissipating material is lowered. Therefore, for example, it is preferable to adjust the content of the filler according to the required thermal conductivity or hardness. The above filler is required to be rapidly formed in the resin composition. It is uniformly dispersed, and if necessary, the content of the resin composition is increased, and the surface treatment can also be carried out by decane treatment or the like. 2226-6964-PF 12 •1293082 In the resin composition of the present invention, hemp MA ^ ^ 'In order to promote the hardening of the resin composition, it may be used to contain a hardening accelerator m A 4. , # ^ , and soil as a hardening accelerator.

Xf is well known, but among them, it is preferable to use the &#;amp; human and & organometallic compounds (hereinafter, pure metal is a compound). In the female AA, I will review the application of the 3rd edition (Sakamoto Chemical Society, Maruzen Co., Ltd.), as long as it has 3Α~7Α, 8,#9P D, the metal element which is not excessive metal element and the metal element belonging to 2B to 6B may be a wide variety, and may be appropriately selected according to the reaction time, the reaction temperature, and the composition of the resin composition. Among them, tin and titanium are preferred, and it is preferable to use a kick of preferably 0. The compound may be used alone or in combination of two or more. Examples of the metal compound of tin include, for example, dibutyltin dilaurate, dibutyltin oxide, diam-acetate, dibutyltin di(2-ethylhexyl), dihexyltin. Diacetate, dioctyltin dilaurate, dimercapto tin bis(isooctyl ethoxide) salt, tin thioate, and the like. As a ί too metal compound, y yfe f, — 籾 籾 举 举 举 钦 钦 钦 钦 钦 钦 钦 钦 钦

Tetraisopropenyl titanate, tetra-propyl titanate, tetrakis(2-ethylhexylhydroxy) titanate, titanium acetylacetate, salt, octene glycol titanate, tetramethyl titanate Salt, triethanolamine titanate, titanium tetraacetylacetonate, and the like. The metal compound is preferably contained in an amount of from 0.001 to 3 parts by mass, more preferably from 0.003 to 2 parts by mass, per 100 parts by mass of the (A) propylene-based polymer (A). 〇. 0054 parts by mass is best. By adjusting the above-mentioned range, the various properties of the obtained heat-receiving material are not lowered, and the effect of promoting the hardening reaction becomes high, and the hardenability and usable time of the resin composition are made. Balance ^

2226-6964-PF 1293082 Ok. Further, the uniformity of the degree of hardening of the obtained heat dissipating material is also high. A hardening accelerator other than the organometallic compound such as a tertiary amine can also be used as necessary to promote the hardening reaction. In the resin composition of the present invention, it is preferred to add water (e.g., ion-exchanged water) in order to promote the hydrolysis of the hydrolyzable strontium sulfonate and to reduce the difference in the degree of hardening of the obtained heat-dissipating material. However, since the fish in the air or the moisture already present in the resin composition (for example, the water contained in the filler causes the hydrolysis to proceed sufficiently, there is no need to add water. The moisture in the resin composition When the amount is less than the equivalent of the hydrolyzable nail fabric in the resin composition, water is added to make the moisture content in the resin composition relative to the hydrolyzable formyl group in the resin composition. Preferably, in the composition of the present invention, it is preferred to add a plasticizer to the 夭Τ M. By using a plasticizer, the heat-dissipating material of the resin composition can be cured by the hardening of the mash. Give more layers of softness.

An anthraquinone which can be used in the present invention, for example, a chlorine-containing plasticizer or an ester oxime plasticizer can be used, for example, a phthalic acid ester such as phthalic acid, or a tetradecyl ester. Aromatic hydrazine in the phase. 广 酉夂 酉夂 酉夂 曰 曰 , , , , , , , , , , , , , , , , , , , , , , , 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸 脂肪酸Plasticizer, liquid rubber, in the case of ^, ^ ^ 隹 $, see below (25C) as a liquid polymer plasticizer (for example, a polymer with a weight average molecular weight of 糸Ύ ^ 刀 ^ 5,000 or less)觜! 1 'With polyester plasticizer ^ ^ propylene enamel plasticizer) and so on. When using this, you can use two or more types together. It is better to use a plasticizer as the plasticizer in the palace, and w to the liquid (25C), and low temperature (for example, 2226-6964-pp 14 1293082 - l〇C or so 'especially in ~2〇 "Abusive,> 仗 π c or so) is also better in liquid form, for example, the freezing point is below W (especially around one or so of paper). Such a plasticizer is excellent for cold, even if It can also maintain the plasticizing effect when used at low temperatures. 'More and more' can be described as a plastic sword, which is a heat-resistant high-quality thing, that is, the mass loss in the case of maintaining 3 hours. ) / The quality before the retention], preferably 5 皙 丨, 丁上, 隹 贝 贝 % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % The best quality is about 0. The use of mass-reducing plasticizers, heat-dissipating materials, and the temperament of the woods can be maintained for a long time. The quality of the plasticizer is reduced by π^^. In the aluminum glass, put the plasticizer ^ Gu,, clothing recorded u. 3 brother, measured in the heating to I5 (TC oven kept 3 small From time to time, the mass reduction is obtained. “〒 The aforementioned plasticizer is for the amount of f, the 丨 main, 7 士 士, and (m) propylene-based polymer (A) is the value of 100 heli injury. %, adding 5 to 4 mussels in the above range does not cause 'recognition of the left and right. By adjusting the softness of the heat dissipating material. %', , the exudation of the material end' can be given to the present invention ( Between the propylene-based abundance starting agent, it is possible to use a block-like poly/I complex (A)' to polymerize using a well-known polymerization method. Μ Polymerization, emulsion polymerization, and the like, in a plasticizer In the polymerization of the plasticizer, the resin composition of the plasticizer can be obtained. The polymerization method of the propylene system is: 'in one process, so it is simple and convenient. When it is, 4 slaves and plasticizers. Additives, etc. of the mixture. Fields, 'This mixture may also be additionally added to the resin composition of the present specification' to add an acidic compound.

2226-6964-PF 15 *1293082 = Adding an acidic compound, for example, it is possible to make the filler quickly and evenly - the knife is scattered, so that the effect of the surviving surviving μ + #田上上, the resin composition is low-viscosity By making the filler of the filler high, the heat dissipation (heat ν) performance of the obtained cured product is increased, and the easy-to-defoaming property of the gas contained in the resin composition can be easily removed. The effect and the effect can be made; the extension of the use time and the effect of the adjustment become easy. ρ as an acidic compound, as long as it is based on the chemical fact sheet π (曰本: 编编# "issued by the company"), which is called acid dissociation hoist), it shows acidity above 1 · 0 (the compound can be, there is no In particular, in order to give full play to the effect of the present invention, it is preferable to use an organic acidified material, particularly a carboxylic acid, and further, it is feared that an acidic compound is caused in the resin composition. In order to cause corrosion of electrical and electronic components, in order to obtain a cured product, the acidic compound used in the hardened material does not remain as a carboxylic acid at a pressure of 2 or less under normal pressure, and in particular, the total carbon number is used. It is better for bismuth 8

The substitution body may be used alone or in combination of two or more. The carboxylic acid having a boiling point of not more than 250 ° C and having a carbon number of 1 to δ is exemplified by formic acid, acetic acid, propionic acid, butyric acid, valeric acid H2-ethylhexanoic acid or the like. Further, in the case where the hardening temperature is 13 〇t θ or 丨, it is preferable to use a carboxylic acid having a boiling point of 170 ° C or lower in the pressure. When the acidic compound is a 100-mass fraction for the (meta)-propanolidine-based polymer (A), the lower limit is preferably in the range of h and 5f, and " The best quality. The upper limit is preferably 5 parts by mass, more preferably 3 parts by mass, and 2 parts by weight of the company. By controlling under the aforementioned

2226-6964-PF .1293082 Limits and upper limit values, the resin composition was found to be low-strengthened by the acidic compound and filled::: Example 2' The air contained in the production of the composition can be easily = Resin resin The resin composition of the present invention can be obtained by a blender, a ball mill, a zebrafish, a refining = _: machine, a training machine, etc., one continuous hand::: no deduction. Further, according to the inside of the apparatus, M can be carried out by heating and enclosing the resin composition as needed. The heat-dissipating material of the invention is stored in the shape of a desired shape, such as a thin official shape or a roll shape, and the shape hardening method and the hardening device are It is not particularly limited to the composition of the composition of the tree (v/yue 曰 composition, which is hydrolyzed by water, and is hydrolyzed according to the air in the air and the necessary water to cause condensation... ^ ^ _ Culture just described the heat-dissipating material, 2 ^, the resin composition can be put into the injection molding die or the batch die 2: hardened into the desired shape, or by the squeezing machine or the sound temple It is obtained by hardening it into a sheet shape, and the curing temperature is m. The core is preferably 15 or less. The thickness of the sheet of the heat-dissipating sheet formed into a sheet shape is preferably at least 1 Å. The heat dissipating material of the present invention is more preferably 5 mm or less, and more preferably 5 mm or less. The heat dissipating material of the present invention is obtained by hardening the resin composition, and the fluidity of the composition is large, meaning that it is in a low state, in addition to the state in which there is no dioxic curing at all, including Only a little fluidity (maltose Or

2226-6964-PF .1293082 asbestos. In the method of using the heat-dissipating material, the resin group 3 can be further modified, for example, to be used between the heat-generating body and the heat-dissipating body, so that the heat-hardening material has a difference in the degree of hardening of the heat-dissipating material. The difference in various physical properties (softness, durability, etc.) tends to be small, and the mass loss of the heat-dissipating material 'in the oven heated to 13 rc for 5 hours is 5% by mass or less. Preferably, it is preferably 2 mass% or less and more k is 2 mass% or less. The smaller the amount of decrease in the amount of f, the softness necessary as the heat-dissipating material 2 can be maintained for a long period of time. The thermal conductivity of the heat dissipating material is preferably set to 5 according to the required performance, and preferably G. 5w/mq to i5w/m • K is more k. The thermal conductivity of the exothermic material can be measured by the rapid thermal conductivity meter QTM-500; manufactured by Kyoto Electronics Manufacturing Co., Ltd.). In the heat dissipating material, in order to improve the strength and workability, etc., it is also possible to use a sound of a resin composition, a person, a film, etc., or an inorganic fiber or an organic fiber, or a resin of the present invention. In the composition, for example, reinforcing fibers, I = a wide range of agents in the field, low polymerization polymerization = organic filler, polymerization low-reducing agent, release agent, freckle cutting agent, wet Turbid dispersing agent, shaking change agent, ultraviolet absorption absorbing;:; external defoaming agent, oxidation preventing agent, dish-based flame retardant, "line Anhua 1 Lu or chlorine oxidation town and other inorganic flame retardant 1# 11 \ gas oxygen magnetic body, anti-static agent, electromagnetic wave (four), dye, crystal soil, high-grade fatty oil, 埶 softening 'paraffin, micro',,,,,,,,,,,,,,

2226-6964-PF 18 12*93082 For the purpose of the invention, any use is possible. The amount of the additive is preferably in an amount that does not deviate from the object of the present invention. Specifically, the total amount of the additives is preferably 100 parts by mass or less based on 1 part by mass of the resin composition. The upper limit of the preferred amount of addition is θ 量, and the upper limit is 8 〇〇. The liquid resin of the present invention is a resin composition for a heat dissipating material containing the (meth) propylene-based polymer (A) as an essential component, after removing the thermally conductive filler (8) from the resin composition for a heat dissipating material of the present invention. . In the liquid resin, various compounds or additives which can be added to the resin composition for a heat dissipating material as described above can be added as necessary. EXAMPLES The present invention will be described in more detail by way of the following examples, but the following examples are not intended to limit the invention, and the present invention is included in the scope of the invention. Within the technical scope. Further, in the examples and comparative examples, "parts" means "mass parts" and "%J means "mass%" unless otherwise specified. Synthesis Example 1 In a vessel equipped with a thermometer, a stirrer, a gas introduction tube, a reflux condenser gas, and a dropping funnel, 39.5 parts of 2-ethylhexyl acrylate was added, and 14 was used as a polymerizable unsaturated machine and a hydrolyzable stone. The ratio of the 7-ring agoxypropyl trioxyloxy group of the calcined base is 0_5 parts (the ratio of the single body having the hydrolyzable formyl group in the whole single body is set to 〇9 mol% "50 parts of a terephthalate as a plasticizer (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name "Adi's home material C880"), as a chain transfer agent, α-methylbenzene 2226-6964~pp 19 1293082 0. 15 parts of the ethylene dimer, and the inside of the container was replaced with nitrogen. 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 〃 Into the; Adi m F funnel, to 1 5 f ^. Further, dimethyl-2,2,__even, Shou Shoulai, ethyl T-based propylene ester) η η was added. The temperature was raised to 90 t and polymerization was carried out for 2 hours. 0·〇3 parts, dibutyltin laurate was added before the end of the polymerization. The metal compound, blown into the air, cools the system to make the polymerization final: organic lipid rafts. By means of a gas chromatograph (hereinafter abbreviated as gc), it remains as a acryl-based polymer having a water-containing hexyl-alkyl group contained in the tree wax A. Horse 39.9%. Obtained

At 25. (: The viscosity is 72〇〇ffipa, s. For the monthly 曰A 0, the average molecular weight measured by GPC, the weight average molecular weight M is Λ 姐 姐 iW Feng · · 6 禺, the average number of eight

Μη is 1 〇·; [10,000. Further, only the outer knife S was used with the U-left calorimeter, and the glass transition temperature of the polymer measured was _61 t. :method

The mass loss of the use of the terephthalate (the above-mentioned agent to make the 〇 夕 夕 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Synthesis Example 2 In a vessel having the same composition as in Synthesis Example 1, 38 parts of 2-ethylhexanoate was charged, and A was put into the right and α was put into the right, and the earthworm was used as the I-compatibility. Machine and adding hydrazine alkyl monolithic body r-ring 4 ι工# 曱 曱 餸 餸 Τ 虱 虱 虱 虱 虱 乳 乳 丙基 ] ] ] ] ] ] 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王The single-body rate of decyl group is 2.8 mol%), the phthalate is used as a plasticizer, 5 〇 = "Adi's C8", as a chain transfer agent - methyl stupid 7 B = 2226-6964 - pp1 20 1293082 Dimer 0.11 parts, except that the resin b was obtained in the same manner as in Synthesis Example 1. 9%。 The amount of the propylene-based polymer having a hydrolyzable zeolitic group contained in the resin b was 39.9%. The obtained resin B had a viscosity at 25 ° C of 68 〇〇 mPa · δ. The molecular weight of the polymer measured by GPC was a weight average molecular weight of 355,000 'number average molecular weight Mng 92,000. Further, the glass transition temperature of the polymer measured by a general method was -60 ° C using a differential calorimeter. Synthesis Example 3 In the gluten UU, ethacrylic acid was added in the same manner as in Synthesis Example 30.3 parts, 9 parts of butyl methacrylate, and as a monomer having a polymerizable machine and a hydrolyzable formyl group. - Epoxy = Oxymethylene Trimethoxy.... 7 parts (with water splitting in the whole monomer: the ratio of the single body of the base is set to 〇·δ mol%), as a plasticizer phthalic acid 50 parts of ester (the aforementioned "Adijia Sucai C88"), as a chain

In addition to the methyl benzoic acid dimer of the carrier, 〇9 ”9 ...", in addition to the example 1, the resin c was obtained. By GC, 斿 、, 戋 之 乙基 乙基 0 0. 1% The amount of water added to the resin C contained in the resin C is 39.9% m to the tree. The hunger is 700 〇mPa*S. The polymerization measured by GPC.八 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均Synthesis Example 4

2226-6964-PF 1293082. In the same synthesis example! In a container, 2-Ethylhexylpropene succinimide 39.85 parts was charged with 7-propoxypropyltrimethoxydecane as a polymerizable unsaturated machine and a hydrolyzable octagonal face. Injury (the ratio of the single body having a hydrolyzable formyl group in a single corpuscle is set to 〇. 27 mol%), and the terephthalate 50 as a plasticizer

: (The above "A|Home stuffed material")" as a key transfer agent, a methyl group, a woman's body, a one-to-one material, 0.5 parts, in addition to the synthesis example 1, the tree is obtained by GC' The residual 2-ethylhexyl acrylate was 〇.丨%, and the amount of the propylene-based polymer having a hydrolyzable formyl group contained in the resin D was 39.9%. The obtained resin D had a viscosity of 62 〇〇mpa at 25t. The molecular weight of the polymer measured by GPC, tongue, number average molecular weight... 2;::=: Differential scanning calorimeter, according to the general method, the glass transition temperature of the polymer is ~ 60 °C. Synthesis Example 5 In a container having the same composition as in the synthesis example, in a container equipped with a thermometer, a stirrer, a gas introduction tube, a reflux condensation gas, and a dropping funnel, 39.4% of 2-ethylhexyl acrylate was added, and hydroxyethyl 6 parts of ruthenium acrylate (the ratio of a single body having a hydroxyl group in Wang Danxing is set to 2.3 moles of phthalate as a plasticizer 5 parts (the aforementioned "Adi Home C880") 'q-methylstyrene dimer 作为· part as a chain transfer agent, replacing the inside of the vessel with nitrogen. The temperature is raised to 75 ° C, and dimethyl-2, 2,-azo as a polymerization initiator is used. 2-Methyl acrylate) 〇 · 1 part and 1 part of benzoate (the above "Adi 2226-6964 ~ pp 22 1293082 slat material C8 80") mixed into the lower funnel, to 丨. After 5 hours, it was added dropwise. Further, a polymerization initiator, dimercapto-2, 2, polyazo (2-mercaptopropenyl) ruthenium·0 3 parts was added, and the temperature was raised to 9 (TC, polymerization was carried out for 2 hours. Add 5 parts of dibutyltin laurate 〇·〇 as an organometallic compound, blow in air, and cool the system to complete the polymerization. Resin oxime was obtained. The residual 2-ethylhexyl acrylate by Gc was 〇·%%, and the amount of the propylene-based polymer having a hydroxyl group contained in the resin oxime was 39.9%. The resin is £25. The viscosity of the crucible is 6i〇〇mpa·b. (4) The molecular weight of the polymer measured by the household weight, the weight average molecular weight is 3:.?: the number average molecular weight Mn is 10,000. χ, using differential scanning The calorimeter has a glass transition temperature of -59 〇C measured by a general method. Synthesis Example 6 In a container having the same composition as in the synthesis example, 'loading methacrylic acid formazan' butyl acrylate § 1G .5 parts 'with r-glycidoxypropyltrimethoxy group as a monomer with a polymerizable unsaturated machine and a hydrolyzable substrate. 8 parts (with water splitting in the whole single body) The ratio of the single body of the sex (4) group is set to G 8 mole %), and as the plasticizer: 50 parts of the present diacid S1 (the aforementioned "Adijia Suqian (10)."), as the chain transfer agent α - Methylstyrene dimer 〇, U·1 injury, in addition to the synthesis example: and she obtained F. The methyl group remaining by GC' Acrylic acid methyl vinegar is 〇·1%, and the amount of the base polymer contained in the resin F is... The second = r:r.firnn pc is in the tree to the moon 曰F at 25. (: The viscosity is 6500 mPa.s. The molecular weight of the polymer measured by GPC is heavy.

2226-6964-PF 1293082 The number average molecular weight Μη is 81,000. The average molecular weight Mw of the polymer measured according to the general method was 341,000, and the glass transition temperature was 37t using a differential scanning calorimeter. Example 1 Resin A1 0 , , , , 々 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子 离子3〇w/m ·κ oxidation of 300 parts (Showa electric eight-way "Shishi system; model AS-10" as heat transfer

V-filled material was mixed with a blender (manufactured by Shisei, Ako Scientific Co., Ltd.; model 600G) to reciprocate 300 rpm and uniformly slashed $8. The resin composition obtained by kneading was allowed to stand at 25 ° C, and the % α defoaming property was determined according to the conditions shown below. The results are shown in Table 1. Next, the following resin composition was defoamed for 5 minutes from the parts of the film, and the thickness of the PET film which was subjected to the treatment of the cut ## 雊孓 was made.

= Set the ± bar coater to coat. The obtained coating material is H 2 small ^ ' Μ to the flaky cured product of the resin composition (the hardenability, initial hardness, softness, adhesion, thermal conductivity, and stagnation resistance of the slab , 0g γ dry I,, and injection--the following conditions are evaluated. The results are shown in Table 1. Example 2 In the first embodiment, except that the resin A was changed to the resin B, the same was true. A resin composition and a sheet-like cured product (heat sink) of the resin composition were obtained. Further, the same evaluation as in Example 1 was carried out, and the results are shown in Table 3, Example 2 2226-6964-PF 24 1293082 In the example 1, the resin composition and the sheet-like cured product (heat sink) of the resin composition were obtained in the same manner except that the resin oxime was changed to the resin C. Further, the same evaluation as in the example 1 was carried out, and the results were shown. In Table 1, in Example 1, except that the resin A was changed to the resin B, more than 2 parts (boiling point 11 9 ° C) was used as the acidic compound, and the rest were the same 埶 / ] a tree such as a composition, and a flaky hardened material of the resin composition (heat dissipation) I. X' was evaluated in the same manner as in Example 1. The results are shown in Table i. Example 5 In the case of Example 1, except that the resin a was changed to the resin, the same as the resin was obtained. And a flake-shaped hard heat sheet of the resin composition). Further, the same evaluation as in Example 1 was carried out, and the results are shown in Table 1. 〇 Comparative Example 1

Resin E1 0 , , , , , , f f f f f f f f f f f ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Acidic vinegar °.43 parts (equivalent to the amount of isocyanate in the field of f-oxygen in the polymer), thermal conductivity of 30W / m · Κ oxidation I Lu 3 0 〇 (Showa Electric Co., Ltd., cloth rabbit AJ garment, model AS-10) was uniformly kneaded as a heat-transfer-type filler in the same manner as in Example 1 of Example 1, and the same as in Example 1, the resin composition and the mouth were obtained. A flaky hardened material (heat sink) of a resin-based compound. Further, the same evaluation as in Example 1 was carried out, and the results are shown in the sheet obtained. In the heat resistance test I, 2226-6964-PF 25 1293082 has a large change in hardness as compared with any of the examples, and a plasticizer is leaked. . Therefore, the result is that there is room for improvement from the point of view of durability. Comparative Example 2 In Example 1, except that the resin hydrazine was changed to the tree wax ρ to obtain the resin composition, and the resin group ', jy ifr, f 3iL ·> the sheet-like cured product (heat release) sheet). Further, the same as #1 & π 贝 of the embodiment, the results are shown in Table 1. The sheet to be served is the result of poor softness of the slab to the hardness of the slab compared to any of the examples. Also, the result is poor with any adhesion. In contrast, the measurement methods and evaluation criteria in each evaluation are shown below. [Available time at 2 5 C] Put an appropriate amount of the obtained resin composition into a beaker and put = to: two? Medium (to prevent water from entering the beaker), use: type value "measuring viscosity during the day" The time when the viscosity is on the initial viscosity of the Japanese gate is the usable time. For example, the longer the 曰t can be used, Then, it can be produced in large quantities at a time, and it is excellent in productivity. [Defoaming property] The resin composition to be served is set to a vacuum of 0.09 MPa minus == wipes, standing for 5 minutes and 5 minutes. By visually observing the package contained in the resin composition

The existence of each sputum. The case where the bubble was not confirmed by visual observation was 〇, and the case where only one point was confirmed by H 4 ^ 皆 was judged as X. For example, when the defoaming operation is performed for a short period of time and no air bubbles are confirmed, the productivity is excellent. [Curability] 2226-6964-ρρ 1293082 The heat sink obtained by heating at loot for 2 hours was evaluated according to the following criteria. i 〇; there are no irregularities or bubbles on the surface of the sheet. No leakage of plasticizer. The thermally conductive filler is uniform without separation and precipitation. The difference in hardness between the surface of the sheet and the central portion is small. Any of the above phenomena are satisfied, and the evaluation is 〇.

X, can confirm the situation of any of the above phenomena. [Initial hardness of the fastener piece] According to JIS Π312, a rubber hardness tester type C (manufactured by Mica Bios Co., Ltd.) was used, and the hardness of the heat sink was measured at the time of hunger. The plate of the hardness tester was pressed against the center of the sample so that the pressure surface was the closest to the sample, and the indicated value was used as the hardness. Further, the sample was used to make the heat sink thick and the base layer. The smaller the value obtained, the more flexible it is. [Softness of the sheet] The heat sink was peeled off from the PET film and completely folded into two portions, and evaluated in the following basis. 〇, when folded into two, there is no crack in the curved part. X; There are cracks in the Bay Area when folded into two. [Adhesiveness of the sheet] The heat sink was pressed back and forth on a 1 kg roller and attached to an aluminum plate. After standing at 25 ° C for 1 hour, the sheet was peeled off from the sheet by hand. The condition is measured by the following criteria. Oh; not easy to peel off. 2226-6964-PF 2Ί 1293082 x , easy to peel off. [Initial thermal conductivity of the sheet] Clip: Rapid thermal conductivity meter (Kyoto Electronics Industry; "QTM-500", p丨2 test material is used to make the heat sink 1 _ thick and the base layer. The measurement was carried out at 25t. [heat resistance]

~ Place the hot film in the oven set to 13 ° C for - hour, measure the mass loss, hardness, and thermal conductivity of the sheet. The mass loss (%) is determined by the method of /[mass before measurement - mass after measurement) / mass before measurement], and is determined by the same method as the initial hardness. The better the resistance (...the initial hardness of the sheet) and the hardness difference (Δ hardness) after the test, the softness is maintained during the long period of time. The thermal conductivity is measured by the same method as the initial thermal conductivity of the sheet. Further, the presence or absence of leakage of the plasticizer after the heat test was judged by visual observation. [Durability] The hardness difference (Δ hardness) of the initial hardness of the heat sink and the sheet hardness after the heat resistance test was evaluated. The smaller the value, the more the flexibility of the sheet can be maintained for a long period of time, so that the contact between the sheet and the heat sink can be maintained for a long period of time, and as a result, the heat generating body can be cooled. The heat transfer efficiency of the body is not lowered, and it has a long-term stable heat release (having durability). Further, the abbreviations used in Table 1 have the following meanings. HDI: hexamethylene diisocyanate A515: defoamer made by Da Chemical Co.; "A-515" 2226~G964"PF 28 1293082 △ Hardness: hardness difference between initial hardness value of sheet and sheet hardness value after heat resistance test [Table 1 EXAMPLES Comparative Example 1 2 3 4 5 1 2 Measurement A 100 Resin B 100 100 Resin C 100 Resin D 100 Resin E 100 Resin F 100 HDI 0.43 A515 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acetic Acid 0.2 Ion Exchange Water 0.1 0.1 0.1 0.1 0.1 0.1 Alumina 300 300 300 300 300 300 300 Defoaming 1 point XXX 〇 XXX 5 minutes 〇〇〇〇〇〇〇 Available time (25t:) 25/J poem 05/j Poetry 25/J Poetry 6 hours 4.0/J Poetry 1.5/J Poetry 3-hour hardening enamel flakes Initial hardness (C hardness) 29 39 30 38 19 38 62 Flake softness 〇〇〇〇〇〇X Foil adhesion 〇〇〇〇 Initial conductivity of bismuth sheet (W/mK) 1.30 1.28 1.26 1.29 1.28 1.28 1.25 Heat resistance (130°C/500 hours) Weight loss (%) 0.41 0.35 0.36 0.37 0.41 0.58 0.44 Sheet hardness (C hardness) 30 42 33 40 21 20 68 Thermal conductivity (ψ/ιη·Κ) 1.31 1.32 1.31 1.28 1.29 1.19 1.24 With or without leakage 4πΤ Black Μ l No or no durability (△ hardness) 1 3 3 --- --- 2 2 18 6 --- As clearly shown in Table 1, in the example of the present invention, it can be obtained efficiently

2226-6964-PF 29 !293〇82

A A resin composition for a heat-dissipating material excellent in hardenability, flexibility, adhesion, thermal conductivity, and durability, and a heat-sensitive material of a cured product thereof. On the other hand, in any of the comparative examples, it is apparent that softness, adhesion, and durability are still room for improvement. The material 'is blended with (meth) propylene-based polymer (A) and thermally conductive. The resin composition for heat-dissipating material of the present invention is filled with (B) decane at a rate of 'and good'.

In the resin composition for a heat dissipating material, (A) has a hydrolyzable group and has a glass transition temperature of 1 (TC or less), and is effective in curing the resin composition for a heat dissipating material excellent in hardenability and workability. Adhesiveness, softness, thermal conductivity, durability, and exothermic materials are also used in the heat dissipation of the Qing, electric and electronic thermal bodies and heat-dissipating blades, and the heat dissipation of the hot plates and metal plates. • Two-worker--, version < between r R, electric components, etc. for heat dissipation. [Figure is not explained briefly], Μ [Main component symbol description]

2226-6964-PF 30

Claims (1)

.##Application Patent Range Revision Amendment date: 96.1.15 Patent application scope: 1. A resin composition for a heat dissipating material, which is obtained by blending a (meth) acryl-based polymer (A) and a thermally conductive filler (B), and is characterized by the above ( The propylene-based polymer (A) has a hydrolyzable formyl group, and the glass transition temperature is below the order, wherein the thermally conductive filler (B) is 3 in the resin composition 1 mu in i%. 〇~go quality%. 2. The resin composition for a heat dissipating material according to the invention of claim 1, wherein the '(a) propylene-based polymer (A) is a composition having a hydrolyzable formyl group in the polymer (4) The unit occupies 0.05 to 5 mol%. 3. A resin composition for a heat-dissipating material of the scope of the application of the patent item 'in which' is further contained in 15 (a plasticizer having a mass loss of less than 5% by mass when the TC is kept for 3 hours. 4. A liquid resin, used The resin composition for a heat-dissipating material according to the ninth aspect of the invention is characterized in that it contains 100 parts by mass of the above-mentioned (meth) propylene-based polymer (A 5 to 400 parts by mass of a plasticizer. The heat dissipating material is characterized in that it is obtained by curing the resin composition for the heat dissipating material of the patent application No. 1 2 2 6-69 64-PF 2. 31