JP2010070717A - Temporary adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a temporary adhesive composition, easy in stripping after completion of processing and having adhesion required in processing. <P>SOLUTION: The temporary adhesive composition includes an epoxy resin and a (meth)acrylic ester monomer, wherein the curing agent component of the epoxy resin and the (meth)acrylic ester monomer are subjected to Michael addition reaction, an amine is contained in the curing agent component of the epoxy resin and the monomer having a (meth)acrylic group has three or more radically-polymerizable unsaturated groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an adhesive composition for temporarily fixing a workpiece to a pedestal for cutting, cutting, grinding or the like.

  Conventionally, temporary fixing adhesives for processing include hot melt resins, water-soluble resins, solvent-soluble resins, alkaline aqueous solution-soluble resins, and acid-soluble resins. These are special compositions, and a special treatment was required for peeling after the completion of processing during bonding. Even general-purpose epoxy adhesive is temporarily fixed, but it cannot be easily removed. In addition, foamed urethane resin may be used as a fast-curing adhesive. However, although the adhesive force is weak and can be easily peeled off, there is a problem that the object during cutting is shifted during temporary fixing.

  Temporary fixing hot melt adhesive for temporarily fixing a work piece at a predetermined position such as a processing table for processing such as grinding, wherein the temporary fixing hot melt adhesive is made of one or more kinds of aliphatic compounds. And the adhesive is solid at room temperature and has a melting point of 50 ° C. or less, is easy to handle and can be fixed for a short time. Is disclosed. (Patent Document 1)

  As an adhesive composition that can be easily re-peeled at room temperature, at least one is a porous body, (A) (a) (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms, 70 to 99. 9% by weight, (b) 0.1 to 10% by weight of a, b-unsaturated carboxylic acid, (c) vinyl excluding (meth) acrylic acid alkyl ester and a, b-unsaturated carboxylic acid 100% by weight of an aqueous emulsion resin containing adhesive polymer microspheres obtained by aqueous suspension polymerization of 0 to 29.9% by weight of a compound in the presence of a protective colloid of incompletely saponified polyvinyl alcohol Parts (B) containing 100 to 1000 parts by weight of organic pigment, and further containing 2000 parts by weight or less of a filler having an oil absorption of 50 ml / 100 g or less are disclosed. That. (Patent Document 2)

The adhesive-cured material has high solubility in water, and when removing a machined small article from temporary fixation, it can be easily removed by simply immersing it in water, and it retains low rash, low toxicity and low odor. As an ultraviolet curable adhesive composition for temporary fixing, a (meth) acrylamide resin component having a water-soluble heterocyclic secondary amine residue, such as acryloylmorpholine, and a photopolymerization initiator, preferably water-soluble light It contains a polymerization initiator and, if necessary, water, and the content ratio between the two components of the resin component and water is not less than 50% by weight of resin and not more than 50% by weight of water. A polymerization initiator added in an appropriate amount is disclosed. (Patent Document 3)
Japanese Patent Laying-Open No. 2005-8780 JP 2005-48078 A JP-A-6-116534

  The problem to be solved is to provide an adhesive composition for temporary fixing that can be easily peeled after completion of processing and has an adhesive force required for processing.

  The invention of claim 1 is a temporary adhesive composition comprising an epoxy resin and a (meth) acrylic ester monomer, wherein the curing agent component of the epoxy resin and the (meth) acrylic ester monomer are Michael-added. Yes, the adhesive stress of temporary bonding can be adjusted.

  The invention according to claim 2 is the temporary adhesive composition according to claim 1, wherein the curing agent component of the epoxy resin contains an amine, and the adhesive stress of the temporary adhesive can be adjusted and the curing time can be adjusted. Is also fast.

  The invention according to claim 3 is the temporary adhesive composition according to any one of claims 1 to 2, wherein the monomer having the (meth) acryl group has 3 or more radically polymerizable unsaturated groups. The peel strength and adhesive strength can be adjusted with a small amount.

  By using the temporary fixing adhesive composition of the present invention, it is possible to adjust the required adhesive force at the time of processing and the peeling force at the end of the work, the processing work contents can be widely applied, and a simple peeling work is achieved.

  The epoxy resin used in the present invention is not particularly limited, and is appropriately selected in consideration of work efficiency, use conditions, etc. in addition to miscibility, curability, adhesiveness, and the like. At the same time, a curing agent is also appropriately selected.

  For example, what is necessary is just to have epoxy groups, such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a reactive diluent. In view of reactivity, hardness, and adhesive strength, it is desirable that there are two or more epoxy groups in the molecule. By these, the basic characteristics of the temporary fixing adhesive composition can be obtained.

  The present invention controls the curing of the epoxy resin by the Michael addition reaction of the (meth) acrylic ester monomer and adjusts the adhesion of the epoxy resin. In the epoxy resin composition, that is, in the curing agent, the (meth) acrylic ester is included. It is characterized by the inclusion of a monomer and Michael addition reaction.

  The Michael addition reaction in the present invention is an addition of a nucleophile to an α, β-unsaturated carbonyl compound. The former is a (meth) acrylic ester monomer and the latter nucleophile is contained in an epoxy resin curing agent. Group, mercapto group and the like, and examples of the curing agent include amine and mercaptan.

As an action of the present invention, a network by Michael addition reaction is formed before the epoxy resin is cured, the curing of the epoxy resin is controlled, and the adhesion and hardness of the epoxy resin material are adjusted. For this reason, three-dimensionalization is indispensable, and the number of functional groups per molecule of the compound serving as the nucleophile of the above-mentioned Michael addition reaction and the carbonyl group per molecule of the (meth) acrylic ester monomer and the resonance structure are not formed. The number of saturated groups is related, and it is desirable that there are a plurality of both.
Epoxy resin curing agents with clear functional groups are not practical from the viewpoint of curing speed and physical properties, and are multifunctional or a mixture of multiple compounds. The number of functional groups and the number of blended parts of the acrylic ester monomer are appropriately selected according to the initial physical properties of the epoxy resin composition.
It is desirable that the number of functional groups of the monomer having a (meth) acrylic group is large and the effect is easily obtained because the number of added parts is small, and that having 3 or more radical polymerizable unsaturated groups has a remarkable effect.

  Examples of epoxy resin curing forms include amines, acid anhydrides, phenols, cationic curing with strong bases, epoxy homopolymerization with amine catalysts, etc., especially those that can be cured at room temperature, desirable.

  A monomer having a (meth) acryl group can be used as long as it has compatibility with an epoxy resin and can be used by curing means such as ultraviolet rays, electron beams, and heat. For example, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, various ethylene oxide, propylene oxide modified products, and the like can be used.

  The adhesive for temporary fixing of the present invention has, as a general form, an epoxy compound as a main ingredient, a monomer having a (meth) acryl group as a main component, and if necessary, a dispersant, a surfactant, a plasticizer, Coupling agents, antifoaming agents, anti-settling agents, fillers, organic solvents, diluents and the like can be blended. For the preparation, a two-component method that is adjusted by a general-purpose mixing means and uses a curing agent component of an epoxy resin as a curing agent can be mentioned as room temperature curing.

  Although the temporary fix | bonded adhesive composition of this invention is not limited to a use, there exists fixation to the base which is a silicon ingot and a fixing jig at the time of a silicon wafer cutting as an example.

  An example will be described below in detail.

  In a container equipped with a stirrer, 100 parts by weight of jER828 (Japan Epoxy Resin Co., Ltd., trade name, epoxy equivalent 184 to 194, specific gravity 1.17, molecular weight of about 370) and DPHA (Nippon Kayaku Co., Ltd., product) Name, 5 parts by weight of dipentaerythritol hexaacrylate) and 105 parts by weight of calcium carbonate A (Sankyo Flour Milling Co., Ltd., trade name, average particle size: 12 μm) as a filler, respectively, and stirred for 1 hour. 36.75 parts by weight of FXJ8077 (Fuji Kasei Kogyo Co., Ltd., trade name, modified aliphatic polyamine) was added and stirred for 3 minutes to obtain an adhesive composition for temporary fixing of Example 1.

  The temporary fixing adhesive composition of Example 2 was obtained in the same manner as in Example 1 except that DPHA of Example 1 was 15 parts by weight, calcium carbonate A was 115 parts by weight, and FXJ8077 was 40.25 parts by weight.

    The adhesive composition for temporary fixing of Example 3 was obtained in the same manner as in Example 1 except that 25 parts by weight of DPHA of Example 1, 125 parts by weight of calcium carbonate A, and 43.75 parts by weight of FXJ8077 were used.

  The same procedure as in Example 2 was conducted except that jER828 of Example 2 was replaced with glycyrol ED-503 (ADEKA Corporation, trade name, 1,6 hexanediol diglycidyl ether) and FXJ8077 was changed to 34.5 parts by weight. No. 4 adhesive composition for temporary fixing.

  The adhesive composition for temporary fixing of Example 5 was carried out in the same manner as in Example 4 except that FXJ8077 of Example 4 was changed to 97.75 parts by weight of Ancamide 2353 (Air Products Japan Ltd., trade name, alicyclic polyamine). It was a thing.

  Adhesive composition for temporary fixing according to Example 6 except that DPHA in Example 2 was replaced with Aronix M-309 (Toagosei Chemical Co., Ltd., trade name, trimethylolpropane triacrylate). It was.

Comparative Example 1
A temporary fixing adhesive composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that DPHA of Example 1 was not used, calcium carbonate A was changed to 100 parts by weight, and FXJ8077 was changed to 35 parts by weight.

Reference example 1
Sister M5250 (Henkel Japan Co., Ltd., trade name, one-component simple foamed urethane) was used as the temporary fixing adhesive composition of Reference Example 1.

Reference example 2
Quick seal 30 (Aika Industry Co., Ltd., trade name, fast-curing mercaptan-based epoxy adhesive) was used as the temporary fixing adhesive composition of Reference Example 2.

Tensile shear adhesive strength: Adhesive area of 3.125 cm between the SUS plates (length 100 mm × width 25 mm × thickness 1.5 mm) of the temporary fixing adhesive compositions of Examples, Comparative Examples and Reference Examples scissors to be ^2, then, 23 ° C., allowed to stand under 3 hours, and the adhesive force measurement sample was measured tensile shear adhesive strength in compliance with JIS K6850. The measured value is an average value of n = 5, and the head speed is 0.3 mm / in with a universal tensile tester 5582 (Instron Japan Co., Ltd.) under the environmental conditions of a temperature of 23 ° C. and a humidity of 50% RH. Carried out in minutes.

  Tensile bond strength: For evaluation of peelability, a JIS A6909 adhesive strength test jig was used, and a 60 mm square 20 mm mortar block (3 in FIG. 159 (Teraoka Seisakusho, 50mm width, base material: warp yarn, weft PET, adhesive strength 8.53N / 25m width) (4 in Fig. 1) Example, Comparative Example, Reference Example Temporary Adhesive Adhesive Composition (1 in FIG. 1) is about 0.1 mm thick, with a 40 mm square stainless steel jig (2 in FIG. 1) as the center. The sample was sandwiched between the stainless steel jigs so as to be in the same direction and allowed to stand for 3 hours at 23 ° C. to prepare a sample. The measured value is an average value of n = 5, and the head speed is 1 mm / min with a universal tensile test machine 5582 type (Instron Japan Co., Ltd.) under the environmental conditions of temperature 23 ° C. and humidity 50% RH. Carried out. The result was interfacial peeling from the cloth tape except that Reference Example 1 was a material failure of the adhesive composition.

Workable time: 100 g of the temporary fixing adhesives of Examples, Comparative Examples, and Reference Examples were constantly stirred under the conditions of a temperature of 23 ° C. and a humidity of 50% RH, and the time when the viscosity increased and the viscosity reached double was measured. .
* 1 Due to foaming in Reference Example 1, confirmation of thickening with a stir bar.

  Tensile bond strength was measured by imposing an appropriate buffer tape on the pedestal, instead of directly bonding to the pedestal, mimicking actual temporary fixing. The requirements for the buffer tape are to maintain the holding force at the time of processing, and it is necessary to achieve both peeling after completion, and the cloth tape is used. The evaluation result in Example 1 is 71% in terms of tensile shear adhesive strength compared to Comparative Example 1, but in terms of tensile adhesive strength, the ratio of the reduction rate of tensile shear adhesive strength to the reduction rate of tensile adhesive strength is 54%. Lowest. Moreover, since the adhesive force required at the time of processing is sufficient in Example 1, it can be appropriately selected within the range of the Example.

It is explanatory drawing of a tensile adhesive strength measurement.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adhesive composition layer 2 Stainless steel jig 3 Mortar block 4 Cloth tape 5 Lower jig 6 Upper shaft 7 Lower shaft

Claims (3)

  A temporary adhesive composition comprising an epoxy resin and a (meth) acrylic ester monomer, wherein the curing agent component of the epoxy resin and the (meth) acrylic ester monomer are Michael-added. The temporary fixing adhesive composition according to claim 1, wherein an amine is contained in the curing agent component of the epoxy resin.   The temporary fixing adhesive composition according to any one of claims 1 to 2, wherein the monomer having a (meth) acryl group has three or more radically polymerizable unsaturated groups.

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