TW546360B - Thermosetting adhesives and adhesive sheets thereof - Google Patents

Abstract

Described is a thermosetting adhesive, which comprises (a) a tack-free polymer obtained from a monomer mixture composed of a (meth)acrylate ester, such as phenoxyethyl (meth)acrylate or nonylphenoxypropyl (meth)acrylate having, as a homopolymer, a glass transition point of -30 DEG C or greater and a monoethylenically unsaturated monomer which is copolymerizable therewith and has a functional group reactive with an epoxy resin; (b) a fluidity imparting resin having a softening point of 80 to 200 DEG C and (c) an epoxy resin; and is substantially free of a hardener for the epoxy resin added as the component (c). The thermosetting adhesive according to the present invention has low tackiness at normal temperatures, does not include air bubbles upon press bonding, permits strong adhesion by the heat treatment under a low pressure in a short time, particularly, within several seconds, is free from inconveniences such as drastic reduction in the adhesion even under continuous use at high temperatures and exhibits high resistance against heat of solder reflow.

Description

V. Description of the invention (1)

JlJiJ member field The present invention relates to an adhesive sheet for fixing an electronic part, which has-containing the thermosetting adhesive agent: ;; '= " In recent years, the use of a variety of bonding materials for fixing requires not only strong adhesion, but also :; 2: the solder reflow in this use has a high degree of heat resistance; ::: base: upward; improve productivity and prevent electronics 4 due to work time In order to meet the above-mentioned needs, the introgression & Agent.埶 Solidity 轺 荖 iq i ^ °, heat treatment hardening thermosetting adhesive d thermal EM adhesive agent due to glass transfer:: 会 会 ::: has a low molecular weight part of the second reaction " Dang heat; Hour = quantity is not wet, so reach in a short time-to improve the residual stress of the adherent due to shrinkage due to shrinkage, when: two :: as soon as the curing and anti-peeling. Regarding this kind of curing shrinkage, Dianji Changzhijian is easy to become B-stage when used), but the Changri Shimen factory needs to consider the initial partial reaction (transfer processing. And long & time plus. Migration bonding treatment is not suitable for short Time has glass transition f :: 4 'Pressure-sensitive adhesives for pressure-sensitive adhesive tapes can be used without preliminary operation; combined with 50 / two n. In addition, it usually does not contain "injection"; storage and properties will not appear Temporal Correlation: :: 89l08366.ptd Page 6 546360

V. Description of the invention (2) ^ Occupied tape contains air bubbles when it is hot-pressed and at a temperature of HOt or above. Due to the expansion of the air bubbles enclosed therein, peeling and blistering occur. In addition, with the right: :: Strength and heat resistance are significantly lower than using adhesive tape with thermosetting adhesive: Man Jj Overview

In view of the foregoing, the object of the present invention is to provide a thermosetting adhesive; it has low adhesion at high temperature, and will not contain 加压 when pressure-bonded: 二 It can obtain strong adhesion in a short time by heat treatment under low pressure. Inferiority: Internal appearance: make the adhesive not to be sharp and inferior when used at high temperature continuously. ^: It has high heat resistance to solder reflow, and it has silk clay II, and contains the thermosetting adhesive. Adhesive sheet. In the course of thorough research on other purposes, when the bamboo shoots were made into acrylic polymers, a kind of "Xinxinmingren" first studied when the alkylenes containing 2 to 14 carbon atoms each The method of obtaining and obtaining is through the use of flat to produce pressure-sensitive adhesive sheet) as Λ ^ earth alkyl acrylate (this ester is usually used in the resulting polymer glass: the mixture is transferred to Λ to the mixture, and Said 夭 ^ early俾 Reduce stickiness, copolymerize to obtain low stickiness: ° ^ reduce fat, etc. to the resulting copolymer. Results

In the case of a monomer containing a burnt base; the adhesive sheet is produced using the monomer containing a burnt base, but the obtained sticky sheet is significantly brittle and the degree becomes -3 (KC or above) Based on the foregoing findings, the inventors have not been satisfied with the flexibility or flexibility. . Adhesive allows two-step study of forming an X-shaped sheet. The results found that heat inherently low adhesion, compression bonding date ^ Tian You write, bend or flexible 'at room temperature> password will not contain air bubbles, can be used at low pressure Down to short

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It is strongly adhered by heat treatment for a period of time, and it will not be closed due to curing when used at high temperature. Even if the continuity is sharply deteriorated, even if the solder is reflowed, it will have excellent reliability; and ; By copolymerization of a (meth) acrylic acid = structure and the main homogeneous polymer has a glass transition temperature _30t, knife resin-a monoethylenically unsaturated monomer with a functional group can initiate cross-linking and A kind of 1 \ ......- ^ one-diameter sign endowment, 7 knives are used to achieve pressure bonding in a short time under low pressure, and an epoxy resin is used as a heat resistance improver, and the present invention is completed. : And then with the user: get a non-sticky copolymer, add a specific additive to the flow weight, so this invention provides a thermosetting adhesive (such as the scope of patent application item 1), which contains a) 100 parts by weight The tacky polymer is obtained from a monomer mixture having a composition of 70 to 99% by weight of a (meth) acrylate, represented by the following formula (1): R1

I (1) CH2 = C-c- (O-R2) n_〇-1 0

II 〇 (where R1 represents a hydrogen atom or a methyl group, R2 represents a methylene group, an ethylene group or a propenyl group, η represents an integer of 1 to 3, and 0 represents a phenyl group, and monoalkyl substituted phenyl or dialkyl substituted benzene Based) with a glass transition temperature of at least -30 ° C and 30 to 1% by weight of a monoethylenically unsaturated monomer when it is a homogeneous polymer.

89108366.ptd Page 8 546360

ίΠ; functional group of oxyresin reaction; printed weight parts denier t ', = # sex resin has a softening point of 80 to 2 0 t: and c) 5 to polymerized and thermosetting than 30 parts of oxyresin a) The application of the above-mentioned light has been exclusively applied to the aforementioned resin, which has a unique structure under low temperature and low viscosity, and has a unique structure and a kind of monoene resin. As A S 't, resin, and adding a port that contains virtually no hardener =). In particular, the present invention relates to another feature that has the aforementioned composition, such as the scope of the patent application, No. 2 where 222 is obtained as an ingredient through exposure to radiation (ie, radiation exposure) such as Zi Li ^ PI ^ 1 Ming. An adhesive sheet (such as the cardia entry) includes a layer of a thermosetting adhesive on one or both sides of the substrate.

St t Γ 'is a thermosetting adhesive which has a temperature of ^ ^^ Station mouth 4 does not contain air bubbles, and can be used at low pressure for short periods of time ϋ: IL ΪForce bonding, especially within a few seconds, even if it is continuous at high ^ 2 ρ2 Due to the residual stress caused by curing shrinkage, adhesion leads to high heat resistance to solder reflow, as well as good guilty properties, and a plug is obtained by copolymerization (A / V obtained from the adhesive sheet of the adhesive) +, Have a glass transition temperature of -30 ° C or above, and then with the obtained 31 ::; can cause cross-linking and-an epoxy tree for low pressure at 2 m plus a specific imparting fluidity and inch There is a constant pressure bonding and a ring is a (meth) acrylic acid mixture represented by the general formula (1). The latter can be copolymerized with the former and has a

Monomer mixtures of the present invention and monoethylenically unsaturated monomers

89108366.ptd Page 9 546360 V. Description of the invention (5) " " ^ Has: a functional group that can react with epoxy resin. Up to 30% by weight (meth) = acrylates can be substituted with vinyl-based monomers, such as vinyl acetate, phenethylhydrazone or acrylonitrile, which are known as modified monomers for acrylic pressure-sensitive adhesives and do not Contains functional groups that can react with epoxy resin, but the amount of substitution is determined according to each monomer _ total category, in order to prevent the resulting adhesive from being caused by the copolymer to decrease and cause stickiness.

The formula (1) indicates that when the (meth) acrylate has a homogeneous polymer, it is not allowed to be 30 C or more, preferably-or more. Typical examples include (meth) acrylic acid, ethoxyethyl, phenoxypropyl (meth) acrylate, nonylphenyl (meth) acrylate, and nonylphenoxypropyl (meth) acrylate. In addition, it is also preferable to use a% oxyethane adduct or a propylene oxide adduct (added mole number: up to 3) such as an ester of phenol, cresol or nonylphenol and (meth) acrylic acid. These esters can be used alone or in combination. In the formula (I), the alkyl portion of the monoalkyl-substituted phenyl or dialkyl-substituted phenyl represented by 0 preferably contains i to 5 carbon atoms. When η of formula (1) is 2 or 3, a plurality of R2 may be the same or different. y is a monoethylenically unsaturated monomer copolymerized with the above-mentioned ester and containing a functional group capable of reacting with an epoxy group to produce a non-sticky polymer and an epoxy resin through copolymerization with the aforementioned ester To improve heat resistance and adhesion. Such monomers include, for example, a carboxyl group-containing monomer, in other words, a carboxyl group as a functional group capable of reacting with an epoxy resin, and a hydroxy group-containing monomer, that is, a monomer containing one hydroxy group as such a functional group. The carboxyl group-containing monomer includes acrylic acid, methacrylic acid, and caprolactone-modified acrylate, and the hydroxyl group-containing monomer includes 2-hydroxy-3-phenoxypropyl acrylate. They can be used individually or in combination. Amine group

JH-OJUU 5. Description of the invention (β) The monomer contains one η ′ ^. The reason is that it is functional with the functional group that reacts with: = and epoxy resin. ^ The reactivity of the heart is too strong and may deteriorate storage stability is better than the single 至 ^ 8 to 99% by weight, compared to the Chinese formula '(fluorenyl) acrylate amount is 7 copolymerization and has a-::: body dosage Wu Zhixin's more didiyl olefinic unsaturated tackiness. The heat-resistance of the thermosetting adhesive obtained by the scale is confirmed, and in the present invention, it is obtained without sticking to A. Although dimerization and the aforementioned monomer mixture can be used in combination or bulk polymerization, the storm polymerization: the two parties, such as bath polymerization ☆, emulsion polymerization, the bulk polymerization is •. 'This side two: J such as external light or electron beam radiation when other poly "methods are used; 2: Polymeric plutonium, which will not be rotten by the residue of organic solvents: such as large electronics, peeling or slipping, And because of = = poor performance or poor water resistance, etc. This is because, Qiaomu adhesion can result in "polymer molecules *" results in non-adhesive polymerization with linear cohesion and particularly excellent heat resistance. A catalyst such as a polymerization initiator or a photopolymerization initiator. The other two are potassium persulfate, ammonium persulfate, hydrogen peroxide, etc., "a redox initiator composed of such a peroxygen reducing agent. The sheep and the thermosetting adhesive according to the present invention are in addition to the viscous polymer a obtained in the aforementioned manner. ), Containing-species endowment and mobility tree age) has a softening point

546360 V. Description of the invention (7) 80 to 2 0 C and an epoxy resin c). Ingredients b) and c) are added after the non-stick polymer is obtained, or added to the monomer mixture before the non-stick polymer is formed. When the monomer mixture is polymerized by exposure to radiation such as ultraviolet light, it is desirable that the components b) and c) are mixed with the monomer mixture and then polymerized. The fluid-imparting resin b) has a softening point (or melting point) of 80 to mo, preferably m to 2000c, and more preferably 120 to 150. . . It is generally known as a sticking agent. Please use, for example, rosin resin, thin knitting, and synthetic petroleum tree: this resin. After adding this kind of fluidity to the interstitial structure, it still obtains firmness. ", Especially a few short-term adhesion is: the softening point of the dynamic resin is lower than 80 ° c for the resin at low temperature and m Γ, but not enough Heat resistance. In terms of e, when the fluidity component is imparted, and it becomes difficult to achieve February; no, the compression is used to complete the adhesion within the amount of the fluid resin. The type of polymer is determined per 100 parts by weight, and it is preferably 5 to 15 parts by weight according to its type or non-sticking weight ratio: When the adhesion polymer is 3 to 30 parts by weight, the resin is pressure-bonded I Acting & Wai. ? If the amount is less than 3 parts by weight, it is difficult to complete it at low pressure in a short time:%] is: and the fluid component ’Therefore: Adhesion at a low pressure in a short time is equal to: weight ratio. 1- Not able to obtain sufficient heat resistance The epoxy resin as component c) is one kind of compound. For example, at least two epoxy-based epoxy resins including bisphenol epoxy resin and bisphenol epoxy resin: "aliphatic epoxy resin, age-specific special grease can be used alone or in combination to make 546360. V. Invention Note (8). When the monomers are mixed, it is determined by the type of this epoxy tree. When the parts by weight and the comparison ratio are not sticky, the result is that the ratio tends to decrease because of the high tendency to decrease. And epoxy resins such as trimethylolpropionate, 1,2-(fluorenyl) acrylate which are polymerized by exposure to radiation and the epoxy resin mixed in the child does not contain a radical which can be polymerized by radiation . The amount of the fat depends on the type and the non-stick polymer relative to 100 parts by weight. The non-stick polymer ranges from 5 to 30, preferably from 5 to 20 parts by weight. When the amount is less than 5 parts, the cross-linking reaction between the viscous polymer and the epoxy resin is insufficient, and the heat resistance = insufficient. In terms of it, when the amount exceeds 30 parts by weight, the hardening adhesive is excessively crosslinked when continuously used, and the adhesion is strong, resulting in damage to reliability. In order to maintain the properties of the adhesive, it is desirable for the heat of the present invention: a cross-linking agent such as an isocyanate compound or an epoxidized p = e ψ ^ meth) acrylate example alkane-C 曱) acrylate, pentaerythrethylene glycol Bis (曱, ^ ^ τ ^ esters. L ^ -based) acrylate or 1,6-hexanediol di-crosslinking agent such as polyfunctional (meth) acrylic acid to make 100 parts by weight The monomer mixture is at the opposite side of 0.05

To 3 parts by weight. When more is used; the ratio is better and better. When using difunctional (meth) acrylic acid vinegar, it is used for more functional groups. In the case of using more functional groups, the amount is adjusted to be slightly larger, and it contains i.咼 The degree of cross-linking after the polymerization tends to be historically inadequate, and it ca n’t be used to meet the needs. Too much, it significantly increases the amount of heat generated, which is quasi-inferior. It is used to cause inferior adhesiveness, such as adhesiveness, elastic modulus of the adhesive, and the thermosetting adhesive in the present invention can:

546360 V. Description of the invention (9) Add conventional additives, softeners, fillers, pigments, raw materials, or optional ingredients, such as plasticizers, known hardeners for epoxy resins, to the extent of quality. However, method f adds amine or polyamine as one of the optional ingredients. In the case of roxazole and monocyanobifluorene, the hardening reaction of epoxy resin with this kind of hardener is carried out before, and the #fixing agent will not be damaged.彡 ^ This kind of hardener will be heat treated. The factory is essentially unpopular, and can only be added when there is stability. The term is used here to have the above-mentioned thermosetting adhesive thermosetting adhesive according to the present invention (the main method is to form two layers by forming one layer-side or both sides and then cutting into 3 pieces = type can be passed, first borrowed ϋ When the polymerization method ί A. The obtainer of this layer is added to it-seeding and fluidity tree two-seed non-sticking, polymer a), parenting agent, etc. to prepare a thermosetting seed & milk resin c), a Agent to the substrate, and if necessary borrowing: 3 U application of the adhesive addition to impart fluid resin b), ring m formation method is through the acid solution to the monomer mixture followed by polyfunctional (methyl) Acrylic, so that a radiation polymerizable additive is added to its partially polymerized material, and the composition obtained by exposure to light, such as ultraviolet light, is applied to the base adhesive heat resistance. Thermosetting adhesion; good 200 micron can be obtained. The special film has a thickness of 10 to 100. Exposure to ultraviolet light is preferably carried out in an oxygen atmosphere or transmissive; Xi == acupuncture gas, etc., and the mixture of monomers or

89108366.ptd 546360 V. Description of the Invention (Yo) Yes, the polymer composition is sprayed without contacting the air. Electromagnetic light emission in the range of 460 nanometers, which has a wavelength longer or shorter than the foregoing wavelength range, has a wavelength. Can be used-general irradiation devices such as amalgam? , External light source, the distance between the external light source and the substance to be exposed or controlled: fixed ,, 'two: = micro-violet intensity 0. i to 7 milliwatts / square centimeter of micro-manufactured The polymer mixture may be lucky, and the polymerization rate of θ is 90% or more. Yada, the substrate includes, for example, a non-release substrate such as a synthetic resin film (such as a fiber-containing substrate and a release substrate such as release paper. The agent layer formed on the release substrate can be finally transferred to the non-release substrate. As for; the base material of the occupant sheet according to this issue includes both non-release base material and release base material. The thermosetting adhesive sheet according to the present invention passes through the aforementioned specific non-adhesive material. The mixture is small enough to impart heat-resistance to the imparted fluid ^ The resin and a small amount of epoxy resin are obtained by initiating a cross-linking reaction with the polymer, so the thermosetting adhesive sheet according to the present invention has low adhesion at room temperature. = No bubbles during compression and bonding. Even under low pressure, it can be strongly adhered within a short period of time, especially within minutes, without inconvenience. For example, even when continuously used at a temperature of not less than 80, it will not be cured. Shrinkage leads to a sharp decrease in adhesive force or residual stress and peeling. It has a high degree of financial and thermal resistance to solder reflow, and it has almost no cross-linking reaction before heat treatment, so it has excellent storage stability. This can be used to use the aforementioned characteristics The variety of uses, such as fixing the electronic component or as heat-resistant film, a metal plate or the like adhesive material.

m 89108366.ptd Page 15 546360 V. Description of the invention (11) All parts in the examples indicate parts. The following will further illustrate the number-to-weight ratio of the present invention. Example 1 The internal length of the reaction state equipped with a condenser tube, nitrogen tube a ^ Ο 1 Λ V, see Lili lice tube, thermometer and stirrer: for 2 10 parts of ethyl acetate you go. Take people t 夂 ^ β As a solvent, 95 parts of phenoxyethyl acrylate θ θ g: -10. 0,5 parts of propionic acid and 0.3 parts of benzene peroxide dioxin second pass mixture were polymerized under a stream of nitrogen, so as to obtain a non-stick polymer solution with a heavy solid content. Using the obtained solution, 5 resins ("XL-22 5L", trade name; Mitsui Toya Chemical Co., Ltd. product, softening point: 85.0, 15 parts of epoxy resin ("Epic〇at ) "828", trade name; Yuka SheU Epoxy Resin Co., Ltd. polyfunctional isocyanate cross-linking agent (individually relative to the solid content per 1,000 parts of solution as a basis t so as to prepare a thermosetting adhesive solution. Then the thermosetting property thus obtained The adhesive solution was applied to a release substrate, followed by drying at 130 t for 5 minutes, thereby forming a thermosetting adhesive layer with a thickness of 100 micrometers. Thus, an adhesive sheet was prepared. Example 2

A four-necked flask was provided with 90 parts of phenoxyethyl acrylate, 5 parts of acrylomethylmorpholine, 5 parts of acrylic acid, and 0.05 part of 2,2-dioxo-2-phenylacetophenone. The resulting mixture was photopolymerized by exposure to ultraviolet light under nitrogen to obtain a syrup having a viscosity of about 30 poises. Using 100 parts of partially polymerized syrup, uniformly mix 5 parts of phenol resin ("XL-2 25L", trade name; ^ Jingdong Ya Chemical Co., Ltd., softening point · 85.0, 15 parts epoxy " resin (Trade name 828 "'Brand name; Yuka Shell Epoxy Co., Ltd.) and 0.3 copies

89108366.ptd page 16 546360 V. Description of the invention (12) 1 '6 hexane monopropionate is used as a crosslinking agent to prepare a photopolymerizable composition. The resulting composition was applied to a release substrate and then photopolymerized by exposure to 900 mJ / cm2 of ultraviolet light. Thus, a thermosetting adhesive layer having a thickness of 1000 μm was formed, and thus an adhesive sheet was prepared. Example 3 In a manner similar to Example 2 but using 90 parts of an oxirane adduct of cresol and acrylic acid (added mole number: 1) (homogeneous polymer Tg: -2) was used instead of 90 parts. Phenoxyethyl acrylate to make an adhesive sheet. Example 4 A four-necked flask was provided with 95 parts of an ester of ethylene oxide adduct of nonylphenol and acrylic acid (added mole number: 1) (homogeneous polymer Tg: -25 ° C), 5 parts of 2-methyl-3-phenoxypropyl acrylate and 0.05 parts of 2,2-dimethoxy-2-phenylphenylethyl g. Same. The resulting mixture was partially polymerized by exposure to ultraviolet light under nitrogen, In this way, a syrup having a viscosity of about 30 poise was obtained. Using 100 parts of a partially polymerized syrup, 10 parts of a terpene resin ("Sumi 1ite resin PR-12603" "was evenly mixed. Name; Sumitomo Durez company product, softening point 1 3 3 C) '10 parts epoxy resin ("Yi Bi buckle 8 1 5", trade name; γ uka

She 1 1 Epoxy Resin Co., Ltd.) and 0.2 parts of trimethylolpropane triacrylic acid. The purpose is to prepare a photopolymerizable composition as a parent crosslinker. The photopolymerizable composition thus obtained was applied to a release substrate, and then exposed to 900 mJ / cm 2 of ultraviolet light to form a 1,000 m thick thermosetting adhesive layer. In this way, an adhesive sheet was prepared. Comparative Example 1 In contrast to a condenser tube, a nitrogen inlet tube, a thermometer, and a stirrer

89108366.ptd Page 17 546360 V. Description of the invention (13) 2 10 parts of ethyl acetate are provided in the reactor as a polymer, Tg: < m, 3 parts of butyl vinegar (all of Benzoic acid is oxidized. The resulting mixture is in a mixture of propionate and propionate and 0.3 parts, a solution of +, ^ θ Α Γ / 占 + 占 σ. Using the resulting solution, 5 parts of phenol resin ( "XL_225L",

Products from Yahua Chemical Co., Softening point: 85t), j 〇σ 'T buckle (Epic〇at) 828 ", trade name. Vnlfa c ^ 衣 乳 树 月 日 (clothing is called 1 on the evening 6t' k Shel 1 ring Produced by Oxygen Resin Co., Ltd .: a solid two-chest cross-linking agent (individually relative to 2,3 $ per 10 ° parts of the solution) as the basis for preparing a thermosetting adhesive solution. Then such a thermosetting adhesive solution is applied to a release substrate = sheet and thus A thermosetting adhesive layer with a thickness of m microns is formed. Thus, in Comparative Example 2 (90 parts of acrylic phenoxy provided by the second firing Λ internal τ, 80 parts of propylene isooctyl ester _ ΛΚ σ g · <~ 3QC), 20 parts of acrylic acid And 0.05 parts of 2,2-diphenylphenylphenylethyl. The resulting mixture was exposed to ultraviolet light under nitrogen. This resulted in a syrup having a viscosity of about 30 poises. Polymerization was performed using 100 Syrup is evenly mixed =; ,, ... Product of Mitsui To pressure Chemical Co., Softening point: 85

Sh / lr-Chen milk resin ("yipu buckle 828" '; trade name; product of Yuka She Dioxy Resin Co., Ltd.) and 03 parts of hexanediol were used to _ X i = compound. The obtained composition was applied to earth material, and then exposed to 900 mJ / cm2 of ultraviolet light. ♦ A thermosetting adhesive layer having a thickness of 100 micrometers was thus formed, and thus obtained.

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A four-necked flask was provided with 80 parts of ethyl acrylate (a homogeneous polymer of &lt;

3 0 C) '15 parts of propylene fluorenylmorpholine, 5 parts of acrylic acid and 0.5 part of 2,2-dimethoxy-2-phenylacetophenone. The resulting mixture was exposed to ultraviolet light under nitrogen to synthesize 'so as to obtain a syrup having a viscosity of about 30 poises (ρ oi es e s). Use 100 parts of partially polymerized syrup to uniformly mix 5 parts of phenol resin ("u-2 2 5 L" 'trade name; product of Mitsui Toya Chemical Co., softening point: 8 5.0), ^ 10 / min ring Oxyresin ("cloth clasp 815", trade name; Yuka Shell ^ Shuyueyue company product) and 0.3 parts of 1,6-hexanediol diacrylate as a cross-linking agent 'thus prepared a photopolymerizable combination Thing. The resulting composition was applied to a release substrate and then photopolymerized by exposure to 900 mJ / cm2 of ultraviolet light. In this way, a thermosetting adhesive layer having a thickness of 1000 μm was formed, and thus an adhesive sheet was prepared. In a manner similar to Example 2 except that 5 parts of phenol resin ("XL-22 5L", trade name; Mitsui Toka Chemical Co., Ltd., softening point: 85 it) were formed to form a thermosetting adhesive layer having a thickness of 1000 microns. Got an adhesive sheet. Compare

In the Song flask, 100 parts of phenoxyethyl acrylate and 0.05 parts of 2, 2-di-f-phenylacetophenone were provided. The resulting mixture was partially polymerized by exposure to ultraviolet light under nitrogen, thus obtaining a syrup having a viscosity of about 30 poise. Use 〇〇〇parts of partially polymerized syrup and mix 丨 〇 parts of terpene phenol resin ("Sumilite; M · Yueyue PR-12630" 'trade name; product of Sumitomo Durez, softening point 1 3 3 ° C), 50 parts epoxy resin (r clothing pin buckle 8 2 8

546360 V. Description of the invention (15)

Guangdong product batch name; YUka Shel 1 epoxy resin company product), 7 modified multi-month female (_ clothing oxygen resin hardener, "ACR. Hardener X-3615, trade name; A 2 1 f:"), And 0 · 3 parts of 1,6-hexanediol triacrylate as a crosslinking agent and a photopolymerizable composition. The photopolymerizable group of people thus obtained was applied to a release substrate, and then exposed to 900 mJ / cm2 violet, 々 = to form a thermosetting adhesive layer with a thickness of 100 microns. In this way, the first example and the first and fifth examples obtained from Examples 1 to 5 depend on the adhesion and solder heat resistance. The results are shown in Table 1. &lt; Appearance after compression bonding &gt; Adhesive sheet cut into 30 mm square cubes was laminated at room temperature by a laminator (kg / cm2, speed: 2 m / min) and sus 3 ^: machine (, degree, time: , Pressure: 5 kg / m2 coated

Said to the end of 7 5 micron polyimide sulfonamide private r 丨 master Y α, from A makeup. The situation of the adhesion zone was visually observed at the pingping site. It was estimated as follows: A: neither air bubbles nor Yiben private # Α of ^ nor ... the non-adhesive part was observed. B: Bubbles or non-adhered parts were clearly observed. &lt; Adhesion &gt;

The adhesive sheet was cut into a width of 10 mm and a length of 5 n ancient t t ^ ^ ^ A, nn 〇r. P; v ^ / length b 〇 house slabs and bad laminator (temperature: 100C, pressure: 5 kg / Square stop + 10,000 mils water, speed: 2 m / min) Laminate a polyimide film with a thickness of 7 5 microns, and then connect # 广 1 .. ^, r X ^ / then the wrong compressor (temperature : 15 0 ° C, time: 1 second, pressure: 5 kg / m2 umbrella, and ^. M ^ y ^ cm wood) bonded to SUS304. After hardening at 150 ° C for 1 hour by heat treatment, a and p at any place p were changed from &gt;, /. All samples were initially left at room temperature for 30 minutes, and then placed at South temperature (at 100 C) for 10 hours, p; r-n ^. / ^^^^ for 100 hours. Then the sample is stretched at a 90-degree angle, and the extension rate of the knife is used, so the center value of the bean is used as the needle for measuring the 90-degree peeling adhesive strength. The U value is set to &lt;

P.20 546360 V. Description of the invention (16) &lt; Solder heat resistance &gt;, Adhesive sheet is cut into small pieces with a width of 10 mm and a length of 50 mm and a laminator (temperature ·· ljO C 'pressure ·· 5 kg / cm², speed ·· 2 m / min) Laminate a polyimide film with a thickness of 75 micrometers, and then use a compressor (temperature ·) to slip C '^ between: 1 second' waste force: 5 kg / square Cm) SUS 3 04 bonded to 30 mm square. Hardened by heat treatment at 15 0 ° C! After the hour, the sample was processed for 60 seconds, and then the surface of SUS 304 was floated upwards at 24 ° Ci fusion welding. The overlap of the sheets after treatment was evaluated by visual observation. Α · = blistering, abnormal adhesion (L (High, enemy lines, peeling off temples) ° B: Obviously observed the aforementioned blistering or abnormal adhesion.

----- Appearance example 1 after closing ------- Example 2 A Example 3 A Example 4 A Comparative example 1 ------------ Comparative example 2 A Comparative example 3 A Comparative example 4 B Comparison Example 5 A Table 1 Adhesive force (g / cm) Allow it to stand at room temperature and leave it to stand at high temperature for 30 minutes. After placing it 1,800 ~~ iTm 2, 600 2, 400 1,800 1,600 1, 200 1, 300 100 50 60 50 20 20 1, 600 1, 400 2, 200 150 Solder heat resistance

A

A

A

B

B

B

B

A

89108366.ptd Page 21 546360 V. Description of the invention (17) From the results shown in Table 1, it is clear that the adhesive sheet does not contain air bubbles and non-stressed forces obtained in Examples 1 to 4 when compressed and bonded, and even if any It is also left at a high temperature; :: Poor with large adhesion and excellent solder heat resistance. The non-adhesiveness of the second song is an example of the poor adhesion of each adhesive sheet. It is incorporated into the ingredients of Comparative Examples 1 to 3 through A, and can provide ❿: Single :: The purpose is to contain neither air bubbles nor bad adhesion, but 'The object f has low adhesion and the heat resistance of the material is unsatisfactory. —The adhesive strength of the sheet was poor and soldered. The adhesive sheet of Comparative Example 4 was unsatisfactory due to deletion and imparted fluidity, and the residue was not high during the compression bonding process, so the solder resisted heat. In the example of the adhesive sheet of Comparative Example 5, the mold was broken and became fat during welding. In addition, the hardening of the epoxy resin and the excessive addition of the epoxy tree gradually progressed. The hardened fruit flakes become unsuitable for use after standing. To reduce adhesion. The examples illustrate the present invention, but industry professionals can make various changes and modifications in accordance with its specific scope. ",,, ..., easy to know has not deviated from its essence and norms 89108366.ptd page 22 546360 Schematic explanation« 89108366.ptd page 23

Claims (1)

546360 // ik- / 豕 J case number 891⑽r.r ^ Lr%-· sl year Two patents issued ta 1 · A thermosetting spotting agent comprising a) one part by weight of 100 parts of a non-stick polymer obtained from a monomer mixture having a composition of 70 to 99 weight percent / Of (fluorenyl) acrylic acid, as shown in the following formula (1):, R1 (1) ch2 = c-watt-(〇-: R2), o-0 〇 (where R1 represents a hydrogen atom or a fluorenyl group , R2 represents methylene, vinyl or acrylic, η represents an integer of 1 to 3 and 0 represents phenyl, monoalkyl-substituted or di-alkyl-substituted benzyl) has glass transition when it is a homogeneous polymer Temperatures of at least -30 ° C and 30 to 1% by weight of monoethylenically unsaturated monomers which are copolymerizable with the former and have functional groups which can react with epoxy resins; b) one of 3 to 30 parts by weight The flowable resin has a softening point of 800 to 2000, and c) a 5 to 30 damage weight ratio bisphenol resin; and an epoxy resin containing no hardener as a component c). 2 · Rushen: The thermosetting adhesive of item i of the Green Patent, where the component a) is non-stick, the polymer is obtained by exposure to radiation. 3 · —A kind of adhesive sheet, a stack of solid materials against the poor ^ +… U adhesive modifier layer, which is included on one or both sides of the substrate, the thermosetting adhesive is white Έ ku ^ The above-mentioned film J contains a) 1 〇 One weight ratio of 0 parts does not stick 7 = two. ίί! A monomer mixture whose composition is 70 to 99 weight (fluorenyl) acrylic acid, which is represented by the following formula ⑴: c: \ Patent case total file delete 8 delete 3 off 9108366 (replace) _] .pte • Brother 24 546360 Case No. 89108366 Λ_ Sixth, the scope of patent application is revised late! . 29 Replacement page R1 I (1) CH2 = CC- (O-R2) n-〇-0 〇 (where R1 represents a hydrogen atom or a fluorenyl group, R2 represents a fluorenyl group, and vinyl or propenyl group 'η represents 1 to An integer of 3 and 0 represent a phenyl group, a mono-substituted phenyl group or a bis-k substituted phenyl group) has a glass transition temperature of at least -30 C and 30 to 1% by weight of a monounsaturated unsaturated monomer when it is a homogeneous polymer It can be combined with the former and has a functional group capable of reacting with epoxy resin; b) one of 3 to 30 parts by weight gives the flowable resin a softening point of 803. Parts by weight of epoxy resin; and adding no hardener. Of =; as component C). 4. If the thermosetting of item 2 of the patent application is UV light. 4 pieces "/, Ding Biping Tianji 5. Rushen: the patent scope! The thermosetting propionate of the item is at least one selected from the group consisting of (V ′) phenoxyethyl propionate, (meth) acrylic acid, (fluorenyl) propionyl phenoxyethyl acetate, (a Group) Ethylene oxide adduct of nonyl (meth) nonyl propionate or propylene oxide;: f = propyl lysine and phenol, orthophenol or nonylphenol. Mission No. 6 of milk propylene burning adduct and (meth) acrylic acid · As in the scope of the patent application, the unsaturated monomer is at least one selected from the group consisting of melamine-containing adhesives, in which one of the monoethylenic groups By. The group consisting of soil and hydroxyl-containing monomers 7. If the fluidity resin assigned to item b) of the scope of the patent application is “b. Turtle turtle tincture”, which is selected from the group consisting of rosin,? sene, synthetic stone surface Page 25 c: \ Master file of patent cases \ 89 \ 89108366 \ 89108366 (replacement) ptc