TW201527473A - Adhesive composition, adhesive sheet, and method for processing adhesive sheet - Google Patents

Abstract

Provided is an adhesive composition including a urethane-based polymer (A) and a filler (B), wherein the average aspect ratio of the filler (B) in the adhesive composition is from 5 to 350. Also provided are: an adhesive sheet having an adhesive layer formed from said adhesive composition; and a method for processing said adhesive sheet. This adhesive sheet having an adhesive layer formed from said adhesive composition has excellent adhesive strength and excellent punchability.

Description

Adhesive composition, adhesive sheet, and processing method of adhesive sheet

The present invention relates to an "adhesive composition" and an "adhesive sheet" (having an adhesive layer formed of the adhesive composition) and a "processing method of an adhesive sheet".

Conventionally, an adhesive sheet having an adhesive layer formed of an adhesive composition is widely used for industrial, commercial, and household use, and is used for adhesion of parts or surface protection applications of parts.

In particular, an adhesive sheet for industrial use has a cutting process or a press working by a blade cutter before being attached to a subject or attached to a subject. Processed into a specified shape.

However, the adhesive sheet having the adhesive layer formed of the adhesive composition containing the urethane-based polymer is suitable for surface protection of the object because the adhesive layer has excellent elastic force. .

However, the adhesive layer containing a urethane-based polymer is high in elasticity, easy to stretch, and easily deformed. Therefore, when the adhesive sheet having the adhesive layer is subjected to cutting processing or press working, etc., the following is true. Shape: One part of the adhesive layer may adhere to the blade and cause "residue of the blade", or the adhesive layer may be formed in the cut surface to bleed out the substrate or the body of the adhesive sheet. situation.

Residue of the blade which is caused by the adhesion of one of the adhesive layers is a factor which reduces productivity such as an increase in the number of times of cleaning of the blade. Further, in the case where the adhesive layer oozes out to the base material or the object to be cut on the cut surface, it is a problem that the quality of the product is lowered in the electronic material parts requiring precision and miniaturization.

In order to solve such a problem, Patent Document 1 proposes an adhesive composition as a material for forming an adhesive layer of an adhesive sheet, which comprises a urethane-based polymer and contains A gelling agent formed of an optically active amino acid derivative having a specific configuration.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-256264

However, in the adhesive composition described in Patent Document 1, a specific gelling agent is an essential component, but the gelling agent causes a decrease in the adhesiveness of the adhesive composition. In fact, the adhesive sheet having the adhesive layer formed by the adhesive composition disclosed in Patent Document 1 as an embodiment has a low adhesive force. Therefore, the viscosity described in Patent Document 1 The composition of the coating is not suitable as an adhesive layer forming material for an adhesive sheet which is required for high adhesion.

Further, the adhesive sheet having the adhesive layer formed of the adhesive composition described in Patent Document 1 cannot be referred to as a base material for sufficiently suppressing the adhesive layer of the cut surface when the press working is performed. Exudation.

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composition which can be used as an adhesive layer forming material for an adhesive sheet, which has excellent adhesion and excellent press workability, and is provided with the adhesive The adhesive sheet of the adhesive layer formed by the composition of the agent, and the processing method of the adhesive sheet.

The present inventors have found that an adhesive composition comprising a urethane-based polymer and a filler can be solved by adjusting the average aspect ratio of the filler dispersed in the adhesive composition to a specific range. The above problems have been accomplished in order to complete the present invention.

That is, the present invention provides the inventions of the following [1] to [16].

[1] An adhesive composition comprising an adhesive composition of a urethane-based polymer (A) and a filler (B), and a filler (B) in the aforementioned adhesive composition The average aspect ratio is 5~350.

[2] The adhesive composition according to the above [1], wherein the length of the long side of the component (B) in the adhesive composition is 0.05 to 2000 μm on average.

[3] The adhesive composition according to [1] or [2] above, wherein (B) The shape of the component is one or more selected from the group consisting of a columnar shape, a cylindrical shape, a spindle shape, a fibrous shape, and a spheroid shape.

[4] The adhesive composition according to any one of [1] to [3] wherein the component constituting the component (B) is selected from the group consisting of a nanocarbon material, a bauxite, and an aluminum hydroxide. And one or more components of the group of diaspore.

[5] The adhesive composition according to any one of the above [1], wherein the content of the component (B) is 0.2 to the total amount of the active ingredient in the adhesive composition. 70.0% by mass.

[6] The adhesive composition according to any one of the above [1], wherein the component (A) is a urethane-based polymer having a polyoxyalkylene group structure.

[7] The adhesive composition according to any one of the above [1], wherein the component (A) is a urethane-based polymer containing a decyl group.

[8] The adhesive composition according to any one of the above [1] to [7] further comprising an adhesion-imparting resin (C).

[9] The adhesive composition according to the above [8], wherein the component (C) is a hydrogenated terpene phenol-based resin.

[10] The adhesive composition according to the above [8], wherein the content of the component (C) is from 30 to 180 parts by mass based on 100 parts by mass of the component (A).

The adhesive composition according to any one of the above [1] to [10], wherein the content of the component (A) is the total amount of the resin component contained in the adhesive composition. It is 40 to 100% by mass.

[12] An adhesive sheet comprising the adhesive layer formed of the adhesive composition according to any one of the above [1] to [11].

[13] The adhesive sheet according to the above [12], which has a structure in which the adhesive layer is held by two release sheets.

[14] The adhesive sheet according to the above [12], which has the above-mentioned adhesive layer on at least one side of the substrate.

[15] The adhesive sheet according to the above [12], which has the above-mentioned adhesive layer on both surfaces of the substrate.

[16] A method of processing an adhesive sheet, which comprises the step of press-working an adhesive sheet according to any one of the above [12] to [15] to a predetermined size.

The adhesive sheet having the adhesive layer formed of the adhesive composition of the present invention has excellent adhesion and excellent press workability, and thus can be suppressed when cutting processing or press working is performed. : the occurrence of a residual edge of the blade caused by the adhesive layer, or the occurrence of bleed out of the substrate or the object to be adhered to the adhesive sheet in the cut surface.

1a, 1b, 1c, 1d‧‧‧ adhesive sheets

2‧‧‧Substrate

3, 3'‧‧‧Adhesive layer

4, 4'‧‧‧ peeling sheets

10‧‧‧Aminoate prepolymer

12‧‧‧The main chain of polymers

14a, 14b‧‧‧ Isocyanate

20‧‧‧ alkylating agent

22‧‧‧Active hydrogen base

24‧‧‧ Hydrolyzable alkylene

26‧‧‧Molecular backbone

30‧‧‧Alkyl-containing urethane-based polymers

32a, 32b‧‧‧ end portion of a urethane-containing urethane-based polymer

Fig. 1 is a cross-sectional view showing an adhesive sheet which is an example of a configuration of an adhesive sheet of the present invention.

Fig. 2 is a view showing a synthesis method and structure of a decyl group-containing urethane-based polymer.

Fig. 3 is a view showing an example of the shape of a filler (B) used in the adhesive composition of the present invention.

Fig. 4 is a view showing an example of the shape of a filler (B) used in the adhesive composition of the present invention.

Fig. 5 is a view showing the shape of a filler used in a comparative example.

6] (a) the adhesive sheet produced in Example 8, (b) the adhesive sheet produced in Comparative Example 3, and (c) the adhesive sheet prepared in Comparative Example 11, after each adhesive sheet was cut by scissors, A photograph of the cut surface of each of the adhesive sheets was observed using a digital microscope (manufactured by KEYENCE, product name "VHX-2000").

[Best Mode for Carrying Out the Invention]

In the following description, "mass average molecular weight (Mw)" is a converted value of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically, a value measured by the method described in the examples. .

In the present invention, the resin component is a polymer having a mass average molecular weight (Mw) of 10,000 or more (however, the filler (B) is not included in the resin component).

Further, for example, the term "(meth) acrylate" is used as a term indicating both "acrylic ester" and "methyl acrylate", and other similar terms are also used.

In addition, the "active ingredient" in the adhesive composition means a component obtained by removing the diluent solvent contained in the adhesive composition, specifically, the components (A) to (F) shown below, Other resin components other than the component (A) and other additives.

[Adhesive composition]

The adhesive composition of the present invention contains the urethane-based polymer (A) and the filler (B), but preferably contains a resin selected from the viewpoint of exhibiting higher adhesiveness. One or more kinds of (C), a crosslinking agent (D), a curing accelerator (E), and a crosslinking assistant (F).

In addition, the adhesive composition of the same aspect of the present invention may contain a resin component other than the above component (A) or other additives other than the above, within a range not impairing the effect.

Hereinafter, each component contained in the adhesive composition of the same state of the present invention will be described.

<(A) component: urethane-based polymer>

The urethane-based polymer (A) used in the present invention is a polymer having at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain. In particular, for example, a urethane-based prepolymer (α) obtained by reacting a polyol (a1) with a polyvalent isocyanate compound (a2), or a urethane-based prepolymer (for the urethane-based prepolymer) may be used. α) Further, a urethane-based polymer (β) obtained by a chain extension reaction using a chain extender (a3) is used.

Among these, the component (A) preferably contains a urethane-based polymer having a polyoxyalkylene structure.

In the present invention, the component (A) may be used singly or in combination of two or more.

Examples of the polyol (a1) include a polyhydric alcohol compound such as an alkanediol, a polyether polyol, a polyester polyol, and a polycarbonate polyol. However, the polyol (a1) is not particularly limited as long as it is a polyol. A bifunctional glycol, a trifunctional triol. Among these polyols (a1), a diol is preferred from the viewpoints of easiness, reactivity, and the like.

Examples of the diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. Alkanediol; alkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; polyalkylene glycol of polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. A polyoxyalkylene glycol such as ethylene glycol, polyoxypropylene glycol or polyoxybutylene glycol. Further, these diols may be used singly or in combination of two or more.

Among these diols, when further reacting with the chain extender (a3), from the viewpoint of suppressing gelation in the reaction, a diol having a mass average molecular weight of 1,000 to 3,000 is preferable.

Examples of the polyvalent isocyanate compound (a2) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-phenylene methane diisocyanate (MDI), and 2,4-toluene diisocyanate. (2,4-TDI), 2,6-toluene diisocyanate Acid ester (2,6-TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4' - phenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethylxylene diisocyanate or the like.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 2, 3-butylidene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

As the alicyclic polyisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate is exemplified. , 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate ), 1,4-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, and the like.

Further, the polyisocyanate compound (a2) may be a modified form of a trimethylolpropane addition type of the above polyisocyanate, a biuret type modified product which reacts with water, and a trimeric isocyanate ring. Trimeric isocyanate type modification.

Among the above-mentioned polyvalent isocyanate compounds (a2), from the viewpoint of obtaining a urethane-based polymer excellent in adhesiveness, it is preferably selected from 4,4'-phenylene methane diisocyanate (MDI). , 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), hexamethylene Diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: isophorone diisocyanate, IPDI) and more than one of these modifications; In view of the above, it is preferably one or more selected from the group consisting of HMDI, IPDI, and the like.

The chain extender (a3) is preferably a compound having two functional groups selected from a hydroxyl group and an amine group, or a compound having three or more functional groups selected from a hydroxyl group and an amine group.

The compound having two functional groups selected from a hydroxyl group and an amine group is preferably at least selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines. One compound.

Examples of the aliphatic diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptane. An alkylene glycol such as an alkanediol such as an alcohol, ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol.

Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.

Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.

Examples of the bisphenol include bisphenol A and the like.

Examples of the aromatic diamine include diphenylmethanediamine, toluenediamine, and xylylenediamine.

Examples of the compound having three or more functional groups selected from a hydroxyl group and an amine group include polyhydric alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and 1-amino-2,3-. Propylene glycol, 1- An amine alcohol such as methylamino-2,3-propanediol or N-(2-hydroxypropylethanolamine) or an ethylene oxide or propylene oxide adduct of tetramethylxylenediamine.

The method for synthesizing the urethane-based prepolymer (α) is not particularly limited. For example, the polyol (a1) and the polyvalent isocyanate compound (a2), and the catalyst added as needed, are placed in a solvent. a method of reacting in a reactor, and the like.

The catalyst to be used is not particularly limited, and examples thereof include a tertiary amine compound and an organic metal compound.

The mixing ratio of the (a1) component and the (a2) component is such that the molar ratio of the NCO group to the OH group ([NCO group] / [OH group]) is preferably from 1.1 to 3.0, and more preferably from 1.2 to 2.5. The way to make its responders better.

Further, in the obtained urethane prepolymer (α), the isocyanate group content (NCO%) is a value measured in accordance with JIS K 1603, preferably 0.5 to 12% by mass, and more preferably Good is 1~4% by mass.

The method for synthesizing the urethane-based prepolymer (α) and the chain extender (a3) to carry out a chain extension reaction to obtain a urethane-based polymer (β) is not particularly limited. For example, the methods described below are listed.

A method in which a solution of a urethane prepolymer (α) is placed in a reactor, and a chain extender (a3) is dropped in the reactor and allowed to react.

‧ A method in which a chain extender (a3) is placed in a reactor, and a solution of a urethane prepolymer (α) is dropped into the reactor and allowed to react.

‧ Put the solution in which the urethane prepolymer (α) is diluted in a solvent into the reactor, and put a specified amount of the chain extender into the reaction at one time. The method in which the device reacts.

Further, in order to terminate the chain extension reaction, a terminal terminator such as a compound having only one active hydrogen reactive with an isocyanate group or a compound having only one amine group may be used.

Examples of the compound having only one active hydrogen reactive with an isocyanate group include monohydric alcohol compounds such as methanol and ethanol.

Examples of the compound having only one amine group include diethylamine, phoflulin, and the like.

(Alkyl group-containing urethane-based polymer)

In the present invention, the "Alkyl group-containing urethane-based polymer" may be contained as the component (A).

The urethane-containing urethane-based polymer preferably has at least one of a main chain and a side chain having at least one of a urethane bond and a urea bond, and has two ends at the main chain. A polymer of a hydrolyzable alkylene group represented by the following general formula (1).

In the above general formula (1), X ¹ and X ² each independently represent a hydroxyl group or an unsubstituted or alkoxy group having a substituent. R ¹ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.

In the above general formula (1), when X ¹ and X ² are alkoxy groups, the alkoxy group preferably has a carbon number of from 1 to 12 from the viewpoint of reactivity of hydrolysis dehydration condensation. It is 1~6, more preferably 1~3, and even more preferably 1~2.

Further, in the general formula (1), the carbon number of the alkyl group represented by R ¹ is preferably from 1 to 12, more preferably from 1 to 6, from the viewpoint of reactivity of hydrolytic dehydration condensation, more preferably 1~3, and more preferably 1~2.

Further, the carbon number of the alkoxy group and the alkyl group does not include the carbon number of the substituent which the group may have.

When the alkoxy group or the alkyl group selected as X ¹ , X ² or R ¹ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group and an amine group.

Next, the molecular structure of the decyl group-containing urethane-based polymer will be described with reference to FIG. 2 .

Fig. 2(a) shows a synthesis example of a urethane-containing urethane-based polymer 30.

First, a urethane prepolymer 10 is prepared which has an isocyanate group 14a, 14b at the end or side chain (not shown) of the main chain 12 of the polymer.

The urethane prepolymer 10 is an urethane prepolymer (α) obtained by reacting the above polyol (a1) with a polyvalent isocyanate compound (a2), and the synthesis method is also Above.

Next, a decylating agent 20 having the active hydrogen group 22 at one end of the molecular main chain 26 and having the hydrolyzability represented by the above general formula (1) at the other end of the molecular main chain 26 is prepared. In the above-mentioned general formula (1), the "active hydrogen group 22" is a group capable of reacting with the isocyanate groups 14a and 14b of the urethane-based prepolymer 10; X ¹ and X ² are a methoxy group and R ¹ is a methyl group.

Then, after the urethane prepolymer 10 and the decylating agent 20 are mixed, for example, a decyl group-containing urethane can be synthesized by reacting at 80 ° C for 1 hour in a nitrogen atmosphere. Polymer 30. Further, it is preferred to carry out the reaction by measuring and confirming that the absorption peak (2265 cm ^-1 ) of the isocyanate group is disappeared by infrared spectroscopy (IR).

Further, as shown in Fig. 2 (b), the decyl group-containing urethane-based polymer 30" is a cross-linking reaction by hydrolysis of a hydrolyzable decyl group represented by the above general formula (1) The hardening is a three-dimensional mesh structure, a so-called moisture-hardening polymer.

Further, in Fig. 2(a), an urethane-based polymer having a fluorenyl group at both ends of the main chain and having a specified fluorenyl group at both ends is exemplified, but the fluorenyl group-containing polymer used in the present invention is used. The urethane-based polymer may be a urethane-based polymer having an alkylene group at the terminal of the hydrolyzable alkylene group represented by the above general formula (1) at the terminal of the side chain.

Further, contrary to the case of Fig. 2(a), a decylating agent having an isocyanate group and a polymer having an active hydrogen group may be reacted to synthesize a decyl group-containing urethane-based polymer.

Further, the urethane-containing urethane-based polymer may be introduced into the urethane bond of the main chain or the side chain or the active hydrogen in the urea bond, as shown in the following examples. Replaced by an organic base.

Therefore, allophanate linkages are also included in the range of urethane linkages, and biuret linkages are also included in the range of urea linkages.

The specific structure of the terminal portions 32a and 32b of the decyl group-containing urethane-based polymer represented by Fig. 2(a) preferably has the following general formulas (2) to (8) (end portion - A) The structure represented by ~G) is preferably a structure represented by the following general formula (2).

In the above general formulas (2) to (8), X ¹ , X ² and R ¹ are the same as the above general formula (1).

In the above general formulas (2) to (5), R ² and R ³ each independently represent an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and the carbon number of the alkyl group is preferably 1~. 12, preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.

Further, the carbon number of the above alkyl group does not include the carbon number of the substituent which the alkyl group may have.

In the above-mentioned general formulas (2) to (5), when the alkyl group selected as R ² and R ³ has a substituent, examples of the substituent include a halogen atom, a cyano group, and a nitro group.

Further, in the above general formula (8), the A system represents an alkylene group, and the The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, still more preferably from 1 to 6.

On the other hand, in the above general formula (8), B represents an organic group having 1 to 20 carbon atoms, and examples of such an organic group include an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms. , unsubstituted or substituted alkylamino group having 1 to 20 carbon atoms, unsubstituted or substituted arylamino group having 6 to 20 carbon atoms, unsubstituted or substituted carbon number 1 Alkoxy group of ~20, unsubstituted or substituted aryloxy group having 6 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted or substituted a heterocyclic group having 2 to 20 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms, unsubstituted or having The substituent has a carbon number of 3 to 20, such as a cycloalkyl group.

The carbon number of each of the above groups does not include the carbon number of the substituent which the group may have.

In the above general formula (8), when the above-mentioned group selected as B has a substituent, examples of the substituent include a halogen atom, a cyano group, and a nitro group.

Further, the structure of the main chain 12 or the side chain (not shown) of the decyl group-containing urethane polymer 30 shown in Fig. 2(a) can be appropriately selected.

However, the oxime group-containing urethane-based polymer used in the present invention is used as a viewpoint of imparting moderate flexibility to the obtained adhesive composition and improving the adhesion to the object. The main chain is preferably A decyl group-containing urethane-based polymer having a polyoxyalkylene structure.

From the above viewpoints, the polyoxyalkylene group is preferably polyoxypropylene or polyoxyethylene, and more preferably polyoxypropylene.

Further, in the above-described decyl group-containing urethane-based polymer, the fluorenyl group-containing urethane-based polymer 30 shown in Fig. 2(a) is used as the side chain. The urethane-containing urethane-based polymerization having the hydrolyzable decyl group represented by the above general formula (1) and having the hydrolyzable decyl group represented by the above general formula (1) at both ends of the main chain Things are better.

As long as the decyl group-containing urethane-based polymer having such a structure is constructed, the crosslinking density of the polymers can be adjusted to a suitable range, and at the same time, the adhesion of the crosslinked adhesive composition is improved. Cohesion.

The mass average molecular weight (Mw) of the component (A) is preferably from 10,000 to 200,000, more preferably from 12,000 to 150,000, more preferably from 15,000 to 100,000, and even more preferably from 20,000 to 70,000.

When the Mw of the component (A) is 10,000 or more, the molecular structure can be prevented from becoming too dense, and the adhesive property of the obtained adhesive composition can be improved. Further, it is possible to avoid a decrease in workability (coatability) due to the viscosity of the adhesive composition being too low.

On the other hand, if the Mw of the component (A) is 200,000 or less, the workability (coatability) of the obtained adhesive composition can be improved. Further, the crosslinking density can be made excessive, and the bubble resistance of the adhesive layer formed of the adhesive composition can be improved.

In the adhesive composition of the same state of the present invention, the content of the component (A) is higher than the total amount of the active component (100% by mass) from the viewpoint of enhancing the adhesiveness of the obtained adhesive composition. The ratio is preferably 15 to 85% by mass, more preferably 20 to 80% by mass, still more preferably 25 to 75% by mass, and still more preferably 30 to 70% by mass.

<Other resin components other than (A) component>

In addition, the adhesive composition of the present invention may contain one or more other resin components other than the component (A) (mass average molecular weight (Mw)) within the range that does not impair the effects of the present invention. More than 10,000 polymers).

In the same manner as the present invention, the total amount of the resin component in the adhesive composition (the total amount (100% by mass) of the other resin components other than the component (A) and the component (A)), (A) The content of the component is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 95 to 100% by mass. %.

When the resin component other than the component (A) is contained, the content of the component (A) is preferably within the above range, and other resin components other than the component (A) are blended.

In addition, as for the adhesiveness of the obtained adhesive composition, the state of the present invention is the same as the total amount (100% by mass) of the active ingredient in the adhesive composition, including (A) The content of the resin component of the component is preferably from 30 to 85% by mass, and more preferably from 35 to 80% by mass. %, more preferably 40 to 75% by mass, and even more preferably 43 to 70% by mass.

The resin other than the component (A) is preferably an acrylonitrile-based polymer from the viewpoint of adjusting the adhesive properties.

The acrylonitrile-based polymer is preferably an acrylonitrile-based polymer having a constituent unit (p1) derived from a (meth)acrylic acid having an alkyl group having 1 to 20 carbon atoms. An alkyl ester; further preferably an acrylonitrile-based copolymer having a constituent unit (p1) and a constituent unit (p2), the constituent unit (p2) derived from a functional group-containing (meth)acrylic acid ester. In addition to the constituent units (p1) and (p2), the acryl-based polymer may have a constituent unit (p3) derived from a monomer other than the above.

Examples of the above (meth)acrylic acid alkyl ester constituting the structural unit (p1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, octadecyl (meth)acrylate, and the like. Further, these alkyl (meth)acrylates may be used singly or in combination of two or more.

Among these, an alkyl (meth)acrylate having an alkyl group having 1 to 8 carbon atoms is preferred, and butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred. ester.

Examples of the functional group-containing (meth) acrylate constituting the structural unit (p2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an epoxy group-containing monomer, and an amine group-containing monomer. A cyano group-containing monomer, a ketone group-containing monomer, a monomer having a nitrogen atom-containing ring, a alkoxyalkyl group-containing monomer, or the like. Still, the functional group-containing monomer can be They may be used alone or in combination of two or more.

Among these, a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having a ring containing a nitrogen atom are preferred.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy(meth)acrylate. a hydroxyalkyl (meth) acrylate such as butyl acrylate, 3-hydroxybutyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; an unsaturated alcohol such as vinyl alcohol or allyl alcohol; .

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, and itaconic acid.

As the monomer having a ring containing a nitrogen atom, for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperidine are mentioned. N-vinylpyrene N-vinylpyrrole, N-vinylimidazole, N-vinylformin, N-vinylcaprolactam, N-(methyl)propenylmercaptoline, and the like.

Examples of the monomer other than the above-mentioned constituent unit (p3) include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isodecyl acrylate, dicyclopentanyl acrylate, and dicyclopentenyl acrylate. A (meth) acrylate having a cyclic structure such as dicyclopentenyloxyethyl acrylate or quinone acrylate, or acrylonitrile or styrene. Further, these monomers may be used singly or in combination of two or more.

The content ratio of the constituent unit (p1) is preferably from 50 to 99% by mass, more preferably from 60 to 97% by mass, even more preferably 70%, based on the total constituent unit (100% by mass) of the acrylonitrile-based polymer. 95% by mass, and better It is 75 to 92% by mass.

The content ratio of the constituent unit (p2) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, even more preferably from 5 to 40% by mass based on the total constituent unit (100% by mass) of the acrylonitrile-based polymer. 30% by mass, and more preferably 8 to 25% by mass.

The content ratio of the constituent unit (p3) is preferably from 0 to 20% by mass, more preferably from 0 to 15% by mass, even more preferably 0%, based on the total constituent unit (100% by mass) of the acrylonitrile-based polymer. 10% by mass, and more preferably 0 to 5% by mass.

The mass average molecular weight (Mw) of the acrylonitrile-based polymer is preferably from 50,000 to 1,500,000, more preferably from 150,000 to 1.2 million, and even more preferably from 300,000 to 1.1 million.

Further, the form of the copolymerization of the acrylonitrile-based polymer is not particularly limited, and may be any block copolymer, random copolymer, or graft copolymer.

The content of the acrylonitrile-based polymer is preferably from 0 to 100 parts by mass, more preferably from 0 to 70 parts by mass, even more preferably from 0 to 60 parts by mass, based on 100 parts by mass of the component (A). Preferably, it is 0 to 25 parts by mass, more preferably 0 to 8 parts by mass.

<(B) component: filler>

The filler (B) used in the present invention is not particularly limited as long as it can be dispersed in the adhesive composition so that the average aspect ratio is 5 to 350.

In the present invention, the term "aspect ratio" means relative to an object The ratio of the length (H) of the long side of the length (L) of the short side of the filler (B), that is, the value calculated by the "length of the long side (H) / length of the short side (L)" . In addition, the "average aspect ratio" refers to the average value of the "aspect ratio" calculated from the ten fillers.

Here, the "length (H)" of the long side of the filler means the length of the filler in the height direction (vertical axis direction).

In addition, the "length (L) of the short side" of the filler means a section having the largest area among the cut surfaces perpendicular to the height direction (vertical axis direction) of the filler, and the section is round or In the case of an ellipse, it means a diameter or a long diameter. When the section is polygonal, it means the length of the longest side among the sides of the polygon.

The value of the "long side length (H)", "short side length (L)", and "aspect ratio" of the specific filler (B) means that it is determined by the method described in the examples. Or calculate the value.

The shape of the filler (B) preferably includes one selected from the group consisting of a columnar shape, a cylindrical shape, a spindle shape, a fibrous shape, and a spheroid shape.

In other words, the shape of the filler (B) may be one only selected from the group of the above-mentioned groups, or may be a combination of two or more types selected from the above group.

Figs. 3 and 4(a) to 4(k) are diagrams showing an example of the shape of the filler (B) used in the adhesive composition of the present invention. Hereinafter, the "long side length (H)" and "short side length (L)" of the respective shapes will be described.

In the cylindrical filler as in Fig. 3(a), the filler The length in the height direction corresponds to the "long side length (H)"; among the cut surfaces perpendicular to the height direction, the diameter of the largest cross section (the oblique portion of Fig. 3(a)) (or The long diameter is equivalent to the length of the short side (L).

Further, in the angular column-shaped filler as shown in Fig. 3(b), the length in the height direction of the filler corresponds to "the length of the long side (H)"; among the cut surfaces perpendicular to the height direction, The length of the longest side among the sides of the polygon having the largest area (the oblique line portion of Fig. 3(b)) corresponds to the "length of the short side (L)".

Further, "the length of the short side (L)", when the polygon is a square, refers to the length of one side of the square; when the polygon is rectangular, it means the longest of the two parallel sides of the rectangle constituting the rectangle. Length (still, the same is true for the following).

Further, in the present invention, the term "columnar" means that the specified plane (for example, the XY plane, the YZ plane, the ZX plane, etc.) has an extensive extent and has a height in a direction perpendicular to the specified plane. shape. In the case of the "columnar", the length of the longest direction among the X direction, the Y direction, and the Z direction is "the length of the long side (H)", and the area of the cut surface perpendicular to the direction is The length of the longest direction in the remaining two directions of the largest section is "the length of the short side (L)".

For example, in the case of a solid as shown in FIGS. 3(a) and 3(b), it has an expansion in the XY plane and a height in a direction (Z direction) perpendicular to the XY plane. In these three-dimensional shapes, the length in the Z direction is longer than the length in both the X direction and the Y direction, so the length in the Z direction corresponds to the "length of the long side (H)". On the other hand, the area of the cut surface perpendicular to the Z direction In the largest section (the oblique line portion of Fig. 3(a)(b)), the longer of the X direction and the Y direction corresponds to the "length of the short side (L)".

Further, in the case of a three-dimensional case as shown in FIG. 4(k), the ZX plane has an expansion and has a height in a direction (Y direction) perpendicular to the ZX plane. In this three-dimensional, the length in the Z direction is longer than the length in both the X direction and the Y direction, so the length in the Z direction corresponds to the "length of the long side (H)". On the other hand, in the section having the largest area among the cut planes perpendicular to the Z direction (the hatched portion of Fig. 4(k)), the longer of the X direction and the Y direction (Fig. 4(k) is The X direction is equivalent to the "length of the short side (L)".

Further, the "columnar shape" in the present invention also includes a three-dimensional shape having a hemispherical shape at at least one end of the column as shown in Fig. 3(c).

In the three-dimensional filler of FIG. 3(c), the length of the filler in the height direction (Z direction) corresponds to "the length of the long side (H)"; perpendicular to the height direction (Z direction) Among the cut surfaces, the diameter (or the long diameter) of the section having the largest area (the oblique line portion of Fig. 3(c)) corresponds to the "length of the short side (L)".

In the cylindrical filler as shown in Fig. 3(d), the length of the filler in the height direction (Z direction) corresponds to "the length of the long side (H)"; perpendicular to the height direction (Z direction) Among the cut faces, the diameter (or the long diameter) of the outermost circle of the largest section (the oblique line portion of Fig. 3(d)) corresponds to the "length of the short side (L)".

Further, in the angular cylindrical filler of the type of the filler of FIG. 3(e), the length of the filler in the height direction (Z direction) corresponds to "the length of the long side (H)"; and the height direction (the Z direction) Among the vertical cut faces, the area with the largest area The length of the longest side among the sides of the outermost polygon of the oblique line portion (Fig. 3(e)) corresponds to the "length of the short side (L)".

In the columnar shape, at least one of the ends in the vertical axis direction has an opening, and the inside is hollow. The shape of the opening portion having the end portion of the opening may be a polygon such as a circle, an ellipse, a hexagon or a quadrangle, and may be the same as or different from the shape of the bottom edge of the column.

In the conical filler of FIG. 3(f), the length of the filler in the height direction (Z direction) corresponds to "the length of the long side (H)"; perpendicular to the height direction (Z direction) Among the cut surfaces, the diameter (or the long diameter) of the section having the largest area (the oblique line portion of Fig. 3(f)) corresponds to the "length of the short side (L)".

Further, in the pyramid-shaped filler as shown in Fig. 3(g), the length in the height direction (Z direction) of the filler corresponds to "the length of the long side (H)"; and the cutting perpendicular to the height direction Among the faces, the length of the longest side among the sides of the polygon having the largest area (the oblique line portion of Fig. 3(g)) corresponds to the "length of the short side (L)".

Further, the term "spindle shape" as used in the present invention means that the specified plane (for example, the XY plane, the YZ plane, the ZX plane, etc.) has an expansion, and has a height in a direction perpendicular to the specified plane, toward the top portion. The shape in which the direction of the broken area gradually becomes smaller.

Therefore, the "spindle shape" in the present invention has a point shape in addition to the top portion of Figs. 3(f) and (g), and includes an upper portion as shown in Fig. 3(h) as a circle and an ellipse. Or a polygonal truncated cone shape.

In the filler of the truncated cone in Fig. 3(h), the length of the filler in the height direction (Z direction) corresponds to "the length of the long side (H)"; perpendicular to the height direction (Z direction) Among the cut faces, the diameter (or long diameter) of the largest section (the shaded portion of Fig. 3(h)), or the length of the largest side of the polygon's side length is equivalent to the "short side" Length (L)".

In the fibrous filler of the type shown in Fig. 4(i), the length of the vertical axis direction (Z direction) of the filler corresponds to "the length of the long side (H)"; and the direction of the vertical axis (Z direction) Among the vertical cut surfaces, the diameter (or the long diameter) of the section having the largest area (the oblique line portion of Fig. 4(i)) corresponds to the "length of the short side (L)".

In the present invention, the term "fibrous" means a shape extending in the direction of the longitudinal axis, and the length of the primary particle in the direction of elongation is larger than the length in the direction perpendicular to the direction of elongation.

Further, as shown in FIG. 4(i), a curved surface may be provided in the longitudinal direction.

In the flat spherical filler of the type shown in Fig. 4(j), the length of the vertical axis direction (Z direction) of the filler corresponds to "the length of the long side (H)"; and the direction of the vertical axis (the Z direction) Among the vertical cut surfaces, the diameter (or the long diameter) of the section having the largest area (the oblique line portion of Fig. 4(j)) corresponds to the "length of the short side (L)".

In the present invention, the term "flat spherical shape" means that the short axis of the ellipse is the rotation axis, and the rotation body obtained when the ellipse is rotated, and the length of the primary particle of the filler in the longitudinal direction (long side) The length (H)) is larger than the length in the direction perpendicular to the longitudinal axis direction (the length (L) of the short side).

Therefore, the true spherical filler like the one shown in Fig. 5(l) is excluded from the filler (B) used in the present invention, and the true spherical shape is the length (H) of the long side (the length in the vertical axis direction). The length of the short side (L) (the length perpendicular to the direction of the longitudinal axis) is the same.

In the present invention, as long as the filler can be dispersed in an average aspect ratio of 5 to 350 in the adhesive composition, the shape of the filler before dispersion is not particularly limited, and is preferably selected from columnar fillers. One or more types of the cylindrical filler, the spindle-shaped filler, the fibrous filler, and the spheroidal filler are preferably selected from the group consisting of a columnar filler and a tubular filler. And one or more of the group of fibrous fillers.

When the adhesive layer is formed from the adhesive composition containing the filler of the above shape, since the fillers easily form a network in the adhesive layer, even if the press-worked fillers are entangled with each other, it is considered to be difficult. Residue of the blade is generated, and the bleeding of the adhesive layer is suppressed, and the press workability is improved. Further, by forming a network of the fillers, the adhesion of the adhesive layer can be kept good, and the adhesion can be improved by the type of the component (A) or the shape of the filler.

In the adhesive composition of the present invention, the average aspect ratio of the filler (B) [length of the long side (H) / length of the short side (L)] is 5 to 350, preferably 6 to 350, and more preferably It is 15 to 340, preferably 25 to 330, more preferably 35 to 320, still more preferably 50 to 310, and even more preferably 60 to 300.

When the average aspect ratio is less than 5, the press workability of the adhesive sheet (which has an adhesive layer formed of the obtained adhesive composition) is When the adhesive sheet is subjected to press working or the like, it can be seen that the blade is left or the adhesive layer is formed on the cut surface to bleed out the substrate or the object to be adhered to the adhesive sheet. Moreover, the adhesion of the adhesive sheet is also lowered.

On the other hand, when the average aspect ratio exceeds 350, the adhesiveness of the resulting adhesive composition is lowered, which is not preferable.

Further, as in the case of the filler of the shape of FIG. 4(l), when the length (H) of the long side and the length (L) of the short side are the same true spherical filler, the above aspect ratio of the filler is 1.

The adhesive composition of the same state of the present invention may also contain a filler of the shape of Fig. 5(l), but the "average" aspect ratio of the filler contained in the adhesive composition must be 5 to 350.

As the state of the present invention, the average length (H) of the filler (B) in the adhesive composition is preferably 0.05 to 2000 μm, more preferably 0.05 to 1000 μm, still more preferably 0.05 to 0.05. 500 μm, more preferably 0.05 to 100 μm, still more preferably 0.07 to 20 μm.

Further, as the state of the present invention, the average length (L) of the short side of the filler (B) in the adhesive composition is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm, more preferably 3.0 to 500 nm, more preferably 5.0 to 100 nm, still more preferably 7.0 to 50 nm.

The average aspect ratio [length of the long side (H) / length of the short side (L)] of the filler (B) before dispersion used in the same state of the present invention is preferably 5 to 450, and more preferably 6~420, more preferably 15~400, more preferably 25~370, more preferably 35~350, even better 50~330, and More preferably, it is 60~310.

The average length (H) of the long side of the filler (B) before dispersion used in the same state of the present invention is preferably 0.05 to 2500 μm, more preferably 0.05 to 1800 μm, still more preferably 0.05 to 800 μm. More preferably, it is 0.05 to 150 μm, more preferably 0.07 to 30 μm.

The average length (L) of the short side of the pre-dispersion filler (B) used in the same state of the present invention is preferably 1.0 to 2000 nm, more preferably 2.0 to 1000 nm, still more preferably 3.0 to 500 nm, and More preferably, it is 5.0 to 100 nm, and more preferably 7.0 to 50 nm.

In the present specification, for example, the "average aspect ratio of the filler (B) in the adhesive composition" means dispersion in the adhesive composition containing the urethane-based polymer (A). The average aspect ratio of the filler (B) is different from the average aspect ratio of the filler (B) before dispersion (before mixing with the urethane-based polymer).

The component constituting the filler (B) is not particularly limited, and is preferably selected from the viewpoint of improving the press workability of the adhesive sheet (which is obtained by using the obtained adhesive composition) while maintaining good adhesion. One or more components selected from the group consisting of free nanocarbon materials, bauxite, aluminum hydroxide, and diaspore; and preferably at least one of a nanocarbon material and a bauxite.

The nanocarbon material is composed of a material containing a graphite flake which has a six-membered ring structure as a main structure, and the graphite structure may contain an element other than carbon such as boron or nitrogen, and the nano carbon material may be In the form of other substances, the nano carbon material can be modified by other conductive substances. The form.

When a nanocarbon material is used as the component (B), a carbon nanotube (CNT) having a tubular shape of a nanocarbon material is preferably used.

The carbon nanotube is a tubular carbon polyhedron having a structure in which a graphite (black lead) sheet (which has a carbon six-membered ring structure as a main structure) and is closed in a cylindrical shape.

The carbon nanotube has, for example, a single-layer carbon nanotube having a structure in which a black lead sheet having one layer is closed to have a cylindrical shape; and a two-layer carbon nanotube having a structure in which two layers of black lead sheets are closed to have a cylindrical shape And a multilayered carbon nanotube having a multilayer structure having three or more concentric cylinders and having a black lead sheet, and any two or more of them may be used in combination.

Further, as the filler (B), when a high aspect ratio nanocarbon material having an average aspect ratio before dispersion of, for example, 500 or more is used, the urethane system is used in the general preparation method of the adhesive composition. The high aspect ratio nanocarbon materials in the polymer (A) are easily entangled with each other, and it is easy to form spherical aggregates having an aspect ratio of less than 5. Therefore, the adhesive composition of the nanocarbon material having an average aspect ratio of 500 or more before dispersion is used, and the dispersion shape of the filler (B) tends to be different from that of the adhesive composition of the present invention.

Therefore, the average aspect ratio of the filler (B) made of the nanocarbon material dispersed in the adhesive composition is adjusted to 5 or more, and the average aspect ratio before dispersion is 450 or less. Carbon materials are preferred.

The average aspect ratio before dispersion of the nanocarbon material is preferably 6 to 420, more preferably 15 to 400, still more preferably 25 to 370, still more preferably 35 to 350, and still more preferably 50 to 50. 330, and even more preferably 60~310.

Still, as filler (B), when using the average aspect ratio before dispersion is In the case of a carbon nanomaterial of 500 or more, for example, mixing with the urethane-based polymer (A), using a stirrer, and stirring by a high number of revolutions (for example, 3000 rpm or more), the agglomerate can be avoided. form.

Further, the bauxite is an alumina-based compound represented by AlO(OH)‧H ₂ O, which is one of alumina hydrates present in nature.

Further, diaspore is an alumina-based compound represented by AlO(OH) as one of minerals present in nature.

Further, as the filler (B), when the nanocarbon material is used, the nanocarbon material is preferably a dispersion liquid from the viewpoint of adjusting the average aspect ratio of the filler in the adhesive composition to the above range. The form is formulated into an adhesive composition containing the urethane-based polymer (A).

When it is formulated into an adhesive composition containing a urethane-based polymer in the form of a dispersion containing a nanocarbon material, since the mixture can be mixed in a low viscosity state, the fillers are easily accessible to each other by formation. The network of fillers thus makes the press workability good.

The solvent of the dispersion is, for example, water or an organic solvent, preferably an organic solvent.

Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, and dimethyl. Formamide, N-methylpyrrolidone, dimethyl alum, and the like.

As a method of preparing a dispersion containing a carbon nanomaterial, for example, a method in which a filler (B) is added to the above solvent, vibration is imparted by ultrasonic waves or the like, and the filler (B) can be dispersed in a solvent.

The solid content concentration of the dispersion containing the nanocarbon material is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, still more preferably 0.1 to 3% by mass.

The content of the component (B) is preferably from 0.2 to 70.0% by mass, more preferably from 0.3 to 50.0% by mass, even more preferably 0.4%, based on the total amount of the active ingredient in the adhesive composition (100% by mass). 15.0% by mass, more preferably 0.5 to 10.0% by mass, still more preferably 0.7 to 6.0% by mass, still more preferably 2.0 to 5.5% by mass.

When the content of the component (B) is 0.2% by mass or more, the press workability of the adhesive sheet (which is obtained by using the obtained adhesive composition) can be improved.

On the other hand, as long as the content of the component (B) is 70.0% by mass or less, good adhesive properties of the adhesive composition can be maintained.

<(C) component: Adhesive resin>

The adhesive composition of the same state of the present invention preferably further comprises an adhesion-imparting resin (C).

The adhesion-imparting resin (C) used in the present invention means a resin having an adhesive property capable of being mixed with the urethane-based polymer (A). The mass-average molecular weight (Mw) of the adhesion-imparting resin is usually less than 10,000, which is different from the resin component containing the component (A).

Further, from the viewpoint of enhancing the adhesiveness of the obtained adhesive composition, the mass average molecular weight (Mw) of the adhesion-imparting resin (C) is preferably from 400 to 4,000, more preferably from 800 to 1,500.

From the viewpoint of improving the adhesiveness of the adhesive composition containing the components (A) and (B), the softening point of the adhesive-imparting resin (C) is preferably 110 ° C or higher, and more preferably 110 to 180 ° C. More preferably, it is 115 to 175 ° C, and more preferably 120 to 170 ° C.

In addition, the "softening point" of the adhesion-imparting resin in the present invention means a value measured in accordance with JIS K 2531.

Examples of the adhesion-imparting resin (C) include rosin-based resins such as rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin-based resins obtained by hydrogenating these rosin-based resins; terpene resins and aromatic modified oximes; a terpene resin such as an ene resin or a terpene phenol resin; a hydrogenated terpene resin obtained by hydrogenating the terpene resin; pentene, isoprene, piperine formed by thermal decomposition of petroleum brain, a C5-based petroleum resin obtained by copolymerizing a C5 fraction such as 1,3-pentadiene and a hydrogenated resin of the C5-based petroleum resin; hydrazine, vinyl toluene, α- or formed by thermal decomposition of petroleum brain A C9-based petroleum resin obtained by copolymerizing a C9 fraction such as β-methylstyrene, and a hydrogenated resin of the C9-based petroleum resin.

Further, in the present invention, the adhesion-imparting resin (C) may be used singly or in combination of two or more kinds of softening points or structures.

Among these adhesion-imparting resins (C), from the viewpoint of enhancing the adhesiveness of the adhesive composition containing the components (A) and (B), a terpene phenol resin is preferred, and hydrazine hydride is preferred. An olefinic phenol resin.

The terpene phenol-based resin used in the present invention is a terpene-based resin of an essential oil component obtained from a natural product such as turpentine or citrus peel, and a copolymer with phenol, and also contains at least a part of the copolymer. Or all hydrogenated hydrogen A terpene phenolic resin.

Further, the hydrogenation ratio of the hydrogenated terpene phenol resin is an unsaturated bond with respect to the terpene phenol resin from the viewpoint of enhancing the adhesiveness of the adhesive composition containing the components (A) and (B). The molar %, preferably 50 mol% or more, is preferably 65 mol% or more, more preferably 80 mol% or more.

The content of the terpene phenol-based adhesion-imparting resin in the component (C) is the total amount of the component (C) from the viewpoint of improving the adhesiveness of the adhesive composition containing the components (A) and (B). (100% by mass), preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.

As a state of the present invention, the content of the component (C) in the adhesive composition is improved relative to (A) from the viewpoint of enhancing the adhesiveness of the adhesive composition containing the components (A) and (B). The component is 100 parts by mass, preferably 30 to 180 parts by mass, more preferably 40 to 170 parts by mass, still more preferably 50 to 160 parts by mass, still more preferably 70 to 150 parts by mass, still more preferably 85 to 130 parts by mass. Parts by mass.

The content of the component (C) relative to the total amount (100% by mass) of the active ingredient in the adhesive composition is preferably from 10 to 70% by mass, and preferably from 15 to 65, from the above viewpoints. The mass% is more preferably 20 to 60% by mass, and more preferably 25 to 55% by mass.

<(D) component: crosslinking agent>

The same adhesive composition of the present invention exhibits higher adhesion From the viewpoint of physical properties, it is preferred to further include a crosslinking agent (D).

Examples of the crosslinking agent (D) include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amine resin system. Crosslinking agent, etc. These crosslinking agents may be used singly or in combination of two or more.

Among these, an isocyanate crosslinking agent is preferred from the viewpoint of further improving the adhesiveness of the obtained adhesive composition.

Examples of the isocyanate crosslinking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, and diphenylmethane-4. 4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, A polyisocyanate compound such as 4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate or lysine isocyanate.

Further, the polyisocyanate compound may be a modified product of a trimethylolpropane addition type of the above compound, a biuret type modified product which reacts with water, or a trimeric isocyanate type modified with a trimeric isocyanate ring. Things.

The content of the crosslinking agent (D) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (A).

<(E) component: hardening accelerator>

In the adhesive composition of the same state of the present invention, when the component (A) contains a "alkyl group-containing urethane-based polymer", the promotion is promoted. It is preferable to further include a hardening accelerator (E) from the viewpoint that the alkylene group-containing urethane-based polymer is cross-linked with each other and further enhances the adhesiveness of the crosslinked adhesive composition. . This hardening accelerator (E) functions as a catalyst.

As the hardening accelerator (E), the cross-linking reaction of the alkylene group-containing urethane-based polymer containing the (A) component is promoted, and the crosslinking density is easily controlled, and the cross-linking is further improved. From the viewpoint of the adhesiveness of the adhesive composition, it is preferably at least one selected from the group consisting of an aluminum-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst.

As the aluminum-based catalyst, aluminum alkoxide, aluminum bismuth, and aluminum (III) chloride are preferable.

As the titanium-based catalyst, titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferred.

As the zirconium catalyst, a zirconium alkoxide, a zirconium chelate compound, and zirconium chloride (IV) are preferable.

As the boron trifluoride-based catalyst, an amine complex or an alcohol complex of boron trifluoride such as boron trifluoride monoethylamine complex is preferable.

The content of the curing accelerator (E) is preferably 0.001 based on 100 parts by mass of the decyl group-containing urethane-based polymer contained in the component (A). ~20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass.

<(F) component: cross-linking aid>

Further, the adhesive composition of the same state of the present invention is as (A) In the case of containing a "alkyl group-containing urethane-based polymer", it is preferred to contain a crosslinking assistant (F) in combination with the above-mentioned curing accelerator (E).

As the crosslinking assistant (F), an alkoxydecane containing an amine group is preferred.

As the amino group-containing alkoxydecane, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and N-2-(aminoethyl)-3-amino group are mentioned. Propylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltri Ethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, and the like.

The content of the crosslinking auxiliary (F) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the decyl group-containing urethane-based polymer contained in the component (A). 0.05 to 6 parts by mass, more preferably 0.1 to 3 parts by mass.

<Other additives>

The adhesive composition of the same state of the present invention can contain other additives in accordance with the use of the adhesive sheet without damaging the effects of the present invention.

As other additives, for example, an ultraviolet absorber, an antioxidant, a softener (plasticizer), a filler, a rust preventive, a pigment, a dye, or the like is exemplified.

When the additives are blended, the amount of the respective additives is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the component (A).

[adhesive sheet]

The adhesive sheet of the present invention is not particularly limited as long as it has an adhesive layer formed of the above-described adhesive composition, and may be an adhesive sheet having a structure in which an adhesive layer is held by two release sheets. It may be an adhesive sheet having an adhesive layer on at least one side of the substrate.

Fig. 1 is a cross-sectional view showing an adhesive sheet of an example of the structure of an adhesive sheet of the present invention.

As a specific configuration of the adhesive sheet in the same state of the present invention, as shown in Fig. 1(a), the "substrate-attached adhesive sheet 1a" having the adhesive layer 3 on one surface of the substrate 2 is exemplified.

Further, as shown in FIG. 1(b), the adhesive layer 1b with the adhesive layer 3 and the adhesive layer 3' on both sides of the substrate 2 may be exemplified; or as shown in the figure As shown in Fig. 1 (c), the adhesive layer 3 is formed on one surface of the substrate 2, and the "substrate-attached adhesive sheet 1c" of the release sheet 4 is laminated on the adhesive layer 3, and the like. Further, in the constitution of the adhesive sheet 1b, the adhesive sheets 3 and 3' may be laminated with the release sheet as an adhesive sheet.

Further, as shown in Fig. 1(d), the substrate may be used without any substrate, and the adhesive layer 3 may be held by the release sheet 4 and the other release sheet 4' as a "substrate-free adhesion". Sheet 1d".

The material of the release sheets 4, 4' of the adhesive sheet 1d may be the same or different, and it is preferable to adjust the material in which the peeling force of the release sheet 4 and the release sheet 4' is different.

For example, the adhesive layer may be provided on one side of a release sheet whose surface is peeled off, and may be curled into a roll shape. Adhesive sheets and the like.

In the adhesive sheet of the same state of the present invention, the thickness of the adhesive layer can be appropriately adjusted depending on the application, etc., preferably 0.5 to 100 μm, more preferably 1 to 60 μm, still more preferably 3 to 40 μm.

The thickness of the adhesive layer is preferably 0.5 μm or more, and exhibits good adhesion regardless of the type of the object to be coated.

On the other hand, if the thickness of the adhesive layer is 100 μm or less, in addition to being advantageous in terms of productivity, when the sheet is made into a wound body, the curling due to deformation of the adhesive layer can be suppressed, or The adhesion of the adhesive layer from the end portion is suppressed, so that it can be a good adhesive sheet in terms of workability.

<Substrate>

The base material of the adhesive sheet which is in the same state of the present invention may be appropriately selected depending on the purpose of use of the adhesive sheet, or may be an insulating base material containing an insulating material, or may be a conductive material containing a genus. Conductive substrate.

Examples of the insulating substrate include, for example, an upper paper (no wood pulp paper), a coated paper, a coated paper, a cellophane, or the like, or a laminated paper in which a thermoplastic resin such as polyethylene is laminated on the paper substrate. Various papers; porous materials such as non-woven fabrics; polyester resins such as polyolefin resins such as polyethylene resins and polypropylene resins; polybutylene terephthalate resins; polyethylene terephthalate resins; a plastic film or sheet formed of an acetate resin, an ABS resin, a polystyrene resin, a vinyl chloride resin, or the like; a plastic film or sheet formed by a mixture of fats; a multi-layer plastic film or sheet having a laminate of such plastic films or sheets.

Further, the substrate such as a plastic film or sheet may be unstretched or stretched in a uniaxial direction or a biaxial direction such as longitudinal or transverse.

Moreover, the base material used in the present invention may further contain an ultraviolet absorber, a photosetter, an antioxidant, an antistatic agent, a slip agent, an anti-caking agent, a colorant, and the like.

Examples of the conductive substrate include a metal foil, a film or sheet in which a metal foil is laminated with a resin forming the insulating base material, and a film obtained by subjecting the surface of the insulating substrate to metal vapor deposition. Or a sheet; a film or sheet obtained by subjecting the surface of the insulating substrate to an antistatic treatment; and a sheet obtained by weaving a metal wire into a mesh shape.

Further, examples of the metal used for the conductive substrate include aluminum, copper, silver, gold, and the like.

The thickness of the substrate is not particularly limited, and is preferably from 10 to 250 μm, more preferably from 15 to 200 μm, still more preferably from 20 to 150 μm from the viewpoint of easy handling.

When the base material is a plastic film or a sheet, it is preferable to perform a surface treatment such as a pre-oxidation method or a roughening method on the surface of the substrate from the viewpoint of improving the adhesion between the substrate and the adhesive layer.

The oxidation method is not particularly limited, and examples thereof include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone. UV irradiation treatment, etc. Further, the unevenness method is not particularly limited. For example, a sand blast method, a solvent treatment method, or the like can be exemplified. These surface treatments can be appropriately selected depending on the type of the substrate, and from the viewpoint of the effect of improving the adhesion to the adhesive layer or the handleability, the corona discharge treatment method is preferred. Also, a primer treatment can be performed.

<Peeling sheet>

Further, the adhesive sheet of the same state of the present invention may be an adhesive sheet having no substrate as described above.

In the adhesive sheet which does not have a base material, a peeling sheet is used instead of the said base material, and when it is used, the peeling sheet is removed.

As the release sheet, a release sheet obtained by peeling treatment on both sides or a release sheet obtained by peeling off one side may be used, and for example, a release agent may be applied to a substrate for a release sheet.

Examples of the base material for the release sheet include a paper base material such as cellophane, coated paper, and upper paper, laminated paper having a thermoplastic resin such as polyethylene laminated on the paper base material, or polyterephthalic acid. A plastic resin film such as a polyester resin film such as an ethylenediester resin, a polybutylene terephthalate resin or a polyethylene naphthalate resin, a polyolefin resin film such as a polypropylene resin or a polyethylene resin, or the like.

Examples of the release agent include a rubber-based elastomer such as a polysiloxane resin, an olefin resin, an isoprene resin, and a butadiene resin, a long-chain alkyl resin, an alkyd resin, and a fluorine resin. Wait.

The thickness of the release sheet is not particularly limited, but is preferably 10 to 200 μm, and more preferably 25 to 150 μm.

[Method of manufacturing adhesive sheet]

The method for producing the adhesive sheet of the present invention is not particularly limited, and it can be produced by a conventional method. For example, an organic solvent is added to the above-mentioned adhesive composition to form a solution of the adhesive composition, and then the solution can be applied to the substrate or the release sheet by a conventional coating method.

However, when the solution of the adhesive composition is adjusted, it is necessary to adjust so that the average aspect ratio of the filler (B) dispersed in the adhesive composition becomes the above range.

Examples of the organic solvent to be added to the adhesive composition include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, and n-propanol. , isopropanol, dimethylformamide, N-methylpyrrolidone, dimethyl alum, and the like.

Further, the organic solvent may be an organic solvent used in the synthesis of the component (A), or an organic solvent used when the component (B) is prepared in the form of a dispersion, may be used as it is, and it may be uniformly coated. In the form of the adhesive solution, one or more organic solvents other than the organic solvent of the dispersion of the component (B) may be added during the synthesis of the component (A).

The solid content concentration of the solution as the adhesive composition is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, still more preferably from 15 to 70% by mass. When the solid content concentration is 5% by mass or more, the amount of use as a solvent is sufficient, and when applied to a substrate or a release sheet, the efficiency of coating and drying is improved, and productivity is improved. The other side In the surface, the solid content concentration is 90% by mass or less, the viscosity is moderate, the coating operation is easy, and the productivity is improved.

Examples of the method of applying the adhesive composition to the substrate or the release sheet include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a roll coating method, and a knife coating method. , die coating method, gravure coating method, and the like.

As a specific manufacturing method, the following method of forming an adhesive sheet is exemplified.

As shown in Fig. 1(a), the adhesive sheet 1a having the adhesive layer 3 on one side of the substrate 2 can be applied, for example, to the surface of one of the substrates 2 to form an adhesive. It is produced by the agent layer 3. Further, after the adhesive sheet 1c of Fig. 1(c) is produced, the release sheet 4 can be removed to form the adhesive sheet 1a.

As shown in Fig. 1(b), the adhesive sheet 1b having the adhesive layers 3, 3' on both sides of the substrate 2 can be applied, for example, directly to both sides of the substrate 2 to form an adhesive layer. 3, 3' and made. Further, two adhesive layers are formed in advance on the release sheet, and two adhesive layers are bonded to both surfaces of the substrate 2, whereby the adhesive sheet 1b can be produced. Further, in this case, the adhesive layer provided on the release sheet is attached to one side of the substrate 2, and the solution of the adhesive composition is directly applied to the other side of the substrate 2 to The adhesive layer is formed, and the adhesive sheet 1b can also be produced.

As shown in Fig. 1(c), the adhesive sheet 3 and the adhesive sheet 1c of the release sheet 4 are sequentially provided on the substrate 2, for example, the release sheet 4 can be laminated. The adhesive sheet of the adhesive sheet 1a obtained as described above was produced. Further, the solution of the above-described adhesive composition is applied directly to the release-treated surface of the release sheet 4 to form the adhesive layer 3, and the adhesive layer 3 is bonded to the substrate 2 to produce the adhesive sheet 1c.

As shown in Fig. 1(d), the adhesive sheet 1d having a structure in which the adhesive layer 3 is held by the two release sheets 4, 4' without using a substrate can be used, for example, the above-mentioned adhesive composition. The solution is directly applied to the release-treated surface of the release sheet 4 to form the adhesive layer 3, and the adhesive layer 3 and the release sheet 4' are bonded together. Further, as described above, the release sheet 4 and the release sheet 4' are preferably adjusted so that the peeling force is different.

Further, after the solution of the adhesive composition is applied onto the substrate or the release sheet to form a coating film, it is preferred to remove the solvent contained in the coating film by a drying treatment.

Further, in order to improve the adhesion, after the drying treatment, it is preferably placed in an environment of, for example, 23 ° C and 50% RH (relative humidity) for about 7 days to 30 days to form an adhesive layer formed from the adhesive composition. (Coating film) is sufficiently crosslinked.

[The physical properties of the adhesive sheet]

The adhesive sheet of the present invention has excellent adhesion.

When the object is stainless steel, the adhesive layer of the adhesive sheet having the thickness of the adhesive layer of 25 μm is preferably 7.0 N/25 mm or more, more preferably 10.0 N/25 mm or more, and more preferably 15.0N/25mm or more, and more preferably 20.0N/25mm or more.

Still, as in the adhesive sheet 1d of Fig. 1(d), when the adhesive sheet is not provided In the case of the structure of the substrate, it is preferred to adjust the adhesion to the polyethylene terephthalate film having a thickness of 50 μm to the above range. Further, the adhesive force of the adhesive sheet means a value measured by the method described in the examples.

[Processing method of adhesive sheet]

The method for processing an adhesive sheet of the present invention has a step of press-working the adhesive sheet of the present invention to a predetermined size.

Since the pressure-sensitive adhesive sheet of the present invention is excellent in press workability, when the press working is performed by the above-described processing method, it is possible to suppress the occurrence of residue of the blade or the adhesion of the adhesive layer to the adhesive sheet on the cut surface. The substrate or the exudation of the object is produced. Therefore, the method for processing an adhesive sheet of the present invention is excellent in productivity, and is suitable as a method for processing an adhesive sheet which is included in the production of electronic material parts requiring precision and miniaturization.

Further, in the method for processing an adhesive sheet of the same state of the present invention, the adhesive sheet attached to the adherend may be subjected to press working, or may be applied to the adhesive sheet before being attached to the subject. Stamping processing.

[Examples]

Regarding the physical properties of the respective components used in the following examples and comparative examples, the values measured by the methods described below were used.

<Aspect ratio of the filler, and long side or particle size>

Using a scanning electron microscope (Hitachi High-Technologies The system name "S-4700"), observe 10 particles of the randomly selected filler, measure the length of each long side and the length of the short side, and set the average of 10 particles as the filler. The length of the long side (H) and the length of the short side (L). Further, the aspect ratio is calculated by "the length of the long side (H) / the length of the short side (L)".

<mass average molecular weight (Mw)>

Using a gel permeation chromatography apparatus (product name "HLC-8020", manufactured by Tosoh Co., Ltd.), the measurement was carried out under the following conditions, and the values measured in terms of standard polystyrene were used.

(measurement conditions)

‧Tube: "TSK guard Column HXL-H" "TSK gel GMHXL (×2)" and "TSK gel G2000HXL" (all manufactured by Tosoh Co., Ltd.)

‧column temperature: 40 ° C

‧Expanding agent: tetrahydrofuran

‧Flow rate: 1.0mL/min

<softening point>

The value measured in accordance with JIS K 2531 was used.

Production Example 1 (Synthesis of a decyl group-containing urethane-based polymer) (1) Synthesis of decylating agent

100 parts by mass of N-aminoethyl-γ-aminopropylmethyldimethoxydecane and 83.5 parts by mass of methyl acrylate were placed in a reaction vessel, and the mixture was stirred at 80 ° C for 10 hours in a nitrogen atmosphere to obtain decane. a decane compound of a chemical.

(2) Synthesis of urethane prepolymer

In a separate reaction vessel from the container used in the above (1), a polyoxypropylene diol (product name "PML S4015", mass average molecular weight: 15,000), 100 parts by mass, and a different Buddha were placed in a polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd.). 2.46 parts by mass of keto diisocyanate (NCO/OH ratio = 1.7) and 0.005 parts by mass of dibutyltin dilaurate were reacted at 85 ° C for 7 hours in a nitrogen atmosphere to obtain a urethane prepolymer.

(3) Synthesis of urethane-containing urethane-based polymer

To 100 parts by mass of the urethane prepolymer obtained in the above (2), 4.21 parts by mass of the decane compound obtained in the above (1) as a decylating agent was added, and the reaction was carried out at 80 ° C under a nitrogen atmosphere. 1 hour. After confirming that the absorption of the isocyanate group (2265 cm ^-1 ) disappeared by IR, the reaction was terminated to obtain a polymer.

The obtained polymer is a decyl group-containing urethane system having a terminal portion represented by the following formula (9) at both ends of the polyoxypropylene of the main chain and having a mass average molecular weight (Mw) of 40,000. polymer.

Further, the decyl group-containing urethane-based polymer is synthesized by using N-aminoethyl-γ-aminopropylmethyldimethoxyanthracene. Since the alkane is used as a raw material of the decylating agent, a bifunctional decyl group is introduced at the terminal as shown by the following formula (9).

Examples 1 to 25 and Comparative Examples 1 to 12 (1) Modulation of adhesive composition

For 100 parts by mass (solid content) of the urethane-based polymer of the type shown in Tables 1 and 2, a filler having the type and the amount (solid content ratio) shown in Tables 1 and 2 is added, Adhesive-imparting resin and various additives (crosslinking agent, hardening accelerator, crosslinking assistant), ethyl acetate as a solvent, and stirring until uniform, a solution of an adhesive composition having a solid concentration of 55 mass% is prepared. . Further, the average aspect ratio of the filler (B) dispersed in the adhesive composition and the average length (H) of the long sides are as shown in Tables 1 and 2.

(2) Production of adhesive sheets

As a substrate, polyethylene terephthalate having a thickness of 50 μm was used. (PET) film (manufactured by Toray Co., Ltd., trade name "Lumirror"), and the ethyl acetate solution of the prepared adhesive composition was applied to one side of the substrate so that the film thickness after drying became 25 μm. Upper to form a coating film.

Then, the coated film was dried and placed in an environment of 23 ° C and 50% RH (relative humidity) for 14 days to sufficiently crosslink the coating film formed from the adhesive composition to produce the same as that of FIG. 1(a). The adhesive sheet 1a is an adhesive sheet having the same configuration.

In the adhesive compositions prepared in the examples and comparative examples described in Tables 1 and 2, the details of the respective components are as follows.

<Aminoate-based polymer (A)>

‧ "US-902A": the product name, manufactured by the company's oil and fat industry (shares), urethane-based polymer, Mw = 56,000.

‧ "Alkyl group-containing urethane-based polymer": The decyl group-containing urethane-based polymer obtained in Production Example 1 had Mw = 40,000.

<Other resin components>

‧ "Acrylhydrazine-based polymer (1)": a methyl acetate solution of an acryl-based polymer obtained by copolymerizing n-butyl acrylate (BA) and acrylic acid (AA), BA/AA = 90.0 / 10.0 (mass parts), Mw: 700,000, solid content concentration: 33.6 mass%.

‧ "Propylene-based polymer (2)": n-butyl acrylate (BA), methyl acrylate (MA), N-propylene hydrazinoline (ACMO), and Methyl acetate solution of propylene fluorenyl polymer obtained by copolymerization of 2-hydroxyethyl acrylate (HEA), BA/MA/ACMO/HEA=80.0/2.0/16.0/2.0 (parts by mass), Mw: 600,000 , solid content concentration: 33.6 mass%.

<filler (B)>

‧ "CNT(1)": trade name "NC 7000", made of Nanocyl, cylindrical multi-layer carbon nanotubes as shown in Fig. 3(d), average aspect ratio (H/L): 150, long side Length (H): 1.5 μm, length of short side (L): 10 nm.

‧ "CNT(2)": product name "VGCF-X", manufactured by Showa Denko Co., Ltd., as shown in Figure 3(d), cylindrical multi-layer carbon nanotubes, average aspect ratio (H/L): 200, length of long side (H): 3.0 μm, length of short side (L): 15 nm.

‧ "Water Alkali": the trade name "CAM 9010", made by Saint-Gobain, as shown in Figure 4(i), fibrous AlO(OH). H ₂ O, average aspect ratio (H/L): 7.2, length of long side (H): 0.09 μm, length of short side (L): 12.5 nm.

‧ "Bon Nitride": trade name "UHP-2", manufactured by Showa Denko Co., Ltd., as shown in Figure 4(k), scaly boron nitride, average aspect ratio (H/L): 3.9, long side Length (H): 11.8 μm, length of short side (L): 3.0 μm.

‧ "Alumina": trade name "AS-20", manufactured by Showa Denko Co., Ltd., as shown in Figure 5(l), true spherical alumina, average aspect ratio (H/L): 1.0, average particle size (=length of long side (H) = length of short side (L)): 22.0 μm.

‧ "Montmorillonite (1)": trade name "ORGANAIT", made by Hojun, the true spherical montmorillonite shown in Figure 5(l), average aspect ratio (H/L): 1.0, average particle size ( = length of long side (H) = length of short side (L)): 2.0 μm.

‧ "Montmorillonite (2)": trade name "S-BEN NX", made by Hojun, the true spherical montmorillonite shown in Figure 5(l), average aspect ratio (H/L): 1.0, average Particle size (=length of long side (H) = length of short side (L)): 1.6 μm.

‧ "cerium oxide": the trade name "MEK-ST-UP", manufactured by Nissan Chemical Co., Ltd., the true spherical organic bentonite shown in Figure 5(l), average aspect ratio (H/L): 1.0, average particle size (=length of long side (H) = length of short side (L)): 12.5 nm.

In the above-mentioned fillers, only the carbon nanotubes were vibrated by ultrasonic waves for 1 hour in an ethyl acetate by an ultrasonic cleaner (42 kHz, 125 W) to disperse them as a solid concentration. 0.3% by mass of the dispersion was added. The filler other than the carbon nanotubes is added directly to other components without being prepared as a dispersion. Moreover, the amount of the filler described in Tables 1 and 2 indicates the amount of the solid content (filler) in the dispersion.

Further, the average aspect ratio of the filler, the length (H) of the long side, and the length (L) of the short side are values before being dispersed (before blending) in the adhesive composition.

<Adhesion-imparting resin (C)>

‧ "YS Polystar NH": manufactured by Yasuhara Chemical Co., Ltd., hydrogenated terpene phenol resin (100 mol% of unsaturated bonds in the molecule, 80 mol% or more is hydrogenation), softening point 125 ° C, Mw: 820.

‧ "YS Polystar G125": manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point 125 ° C, Mw: 1080.

<Crosslinking agent (D), hardening accelerator (E), crosslinking assistant (F)>

‧ "Crosslinking Agent": Nippon Polyurethane Industry, trade name "CORONATE HX", isocyanate crosslinking agent (trimeric isocyanate type modified product of hexamethylene diisocyanate).

‧ "hardening accelerator": boron trifluoride monoethylamine complex.

‧ "Crosslinking Aid": 3-Aminopropyltrimethoxydecane.

The adhesion and press workability of the adhesive sheets produced in the examples and the comparative examples were measured and evaluated by the following methods. The results are shown in Tables 1 and 2.

<adhesion>

The prepared adhesive sheet was cut into 25 mm × 300 mm to be used as a test piece.

The test piece was attached to a stainless steel plate (SUS304, No. 360 grinding) under the environment of 23 ° C and 50% RH (relative humidity), and left in the same environment for 24 hours, 24 hours after attachment, according to JIS Z0237. :2000 Determines the stickiness of the adhesive sheet by the 180° peeling method at a pulling speed of 300 mm/min. Focus on.

<Stamping workability>

The prepared adhesive sheet was cut with a pair of scissors, and the cross section of the adhesive sheet was observed using a digital microscope (manufactured by Keyence Corporation, product name "VHX-2000"), and evaluated by the following criteria.

A: On the scissors used for the cutting of the adhesive sheet, the adhesion of the adhesive layer was not observed, and the boundary between the substrate and the adhesive layer was clear, and the exudation of the adhesive layer to the substrate portion was not observed.

B: Adhesion of the adhesive layer was confirmed on the scissors used for cutting the adhesive sheet, and it was confirmed that a small amount of the adhesive layer was peeled off or the adhesive layer was oozing out to the substrate portion.

C: Adhesion of the adhesive layer was confirmed on the scissors used for cutting the adhesive sheet, and it was confirmed that many adhesive layers were peeled off or the adhesive layer was oozing out to the substrate portion.

As can be seen from Table 1, the adhesive sheets produced in Examples 1 to 25 were excellent in adhesion and press formability.

On the other hand, as shown in Table 2, the adhesive sheets produced in Comparative Examples 1 to 12 were all inferior in press workability.

Fig. 6 is a photograph of a cut surface of each of the adhesive sheets after the adhesive sheet was cut by scissors using a digital microscope (manufactured by KEYENCE, "VHX-2000"), and (a) is produced in the same manner as in Example 8. (b) is a photograph of the cut surface of the adhesive sheet prepared in Comparative Example 3; (c) is a photograph of the cut surface of the adhesive sheet prepared in Comparative Example 11. In the photographs (a) to (c) of Fig. 6, the adhesive sheet is on the right side and the pedestal on the left side, and the cut portion is photographed from the side of the substrate.

Fig. 6(a) shows the cut surface of the adhesive sheet produced in the eighth embodiment, and the boundary between the substrate and the adhesive layer is clear, and it is known that a part of the adhesive layer is oozing out to the outside. The press workability of the adhesive sheet is good.

On the other hand, in the cut surface of the adhesive sheet prepared in Comparative Examples 3 and 11 of Figs. 6(b) and (c), a part of the adhesive layer was exuded to the outer substrate portion, and the adhesion was known. The sheet has poor press workability.

[Industry Utilization]

The adhesive sheet having the adhesive layer formed of the adhesive composition of the present invention has excellent adhesiveness and excellent press workability, and therefore requires precision in, for example, electronic material parts, and press processing is necessary. For use, it is suitable for use.

Claims (16)

An adhesive composition comprising an adhesive composition of a urethane-based polymer (A) and a filler (B), and an average aspect ratio of the filler (B) in the adhesive composition is 5~350. The adhesive composition according to claim 1, wherein the length of the long side of the component (B) in the adhesive composition is 0.05 to 2000 μm on average. The adhesive composition according to claim 1 or 2, wherein the shape of the component (B) is one or more selected from the group consisting of a columnar shape, a cylindrical shape, a spindle shape, a fibrous shape, and a spheroid shape. The adhesive composition according to claim 1 or 2, wherein the component (B) is one or more selected from the group consisting of a nanocarbon material, a bauxite, an aluminum hydroxide, and a diaspore. ingredient. The adhesive composition according to claim 1 or 2, wherein the content of the component (B) is 0.2 to 70.0% by mass based on the total amount of the active ingredient in the adhesive composition. The adhesive composition according to claim 1 or 2, wherein the component (A) is a urethane-based polymer having a polyoxyalkylene structure. The adhesive composition according to claim 1 or 2, wherein the component (A) is a urethane-based polymer containing a decyl group. The adhesive composition of claim 1, which further comprises an adhesion-imparting resin (C). The adhesive composition of claim 8, wherein the component (C) is a hydrogenated terpene phenol resin. An adhesive composition according to claim 8 or 9, wherein The component (A) is 100 parts by mass, and the component (C) is contained in an amount of 30 to 180 parts by mass. The adhesive composition of claim 1 or 2, wherein the content of the component (A) is 40 to 100% by mass based on the total amount of the resin component contained in the adhesive composition. An adhesive sheet having an adhesive layer formed of the adhesive composition of any one of claims 1 to 11. An adhesive sheet according to claim 12, which has a structure in which the above-mentioned adhesive layer is held by two release sheets. The adhesive sheet of claim 12, which is attached to at least one side of the substrate and has the aforementioned adhesive layer. The adhesive sheet of claim 12, which has the aforementioned adhesive layer on both sides of the substrate. A method of processing an adhesive sheet, comprising the step of press-working an adhesive sheet of any one of claims 12 to 15 to a specified size.