KR101775652B1 - Composition for substrate layer - Google Patents
Composition for substrate layer Download PDFInfo
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- KR101775652B1 KR101775652B1 KR1020160002808A KR20160002808A KR101775652B1 KR 101775652 B1 KR101775652 B1 KR 101775652B1 KR 1020160002808 A KR1020160002808 A KR 1020160002808A KR 20160002808 A KR20160002808 A KR 20160002808A KR 101775652 B1 KR101775652 B1 KR 101775652B1
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- thermally expandable
- expandable microspheres
- composition
- acrylate
- base layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a composition for producing a base layer. The composition for preparing a base layer of the present invention is characterized by having excellent properties such as cold resistance, heat resistance, durability, shock absorbability and resistance against spallation and excellent gap adhesion with an adherend as it includes thermally expandable microspheres.
Description
The present invention relates to a composition for producing a base layer.
BACKGROUND ART An acrylic foam tape having a substrate layer is used in portable electronic devices such as mobile phones and portable game machines and electronic devices such as televisions and displays for personal computers. For example, in Korean Patent Laid-Open Publication No. 2008-0060544, an acrylic pressure-sensitive adhesive layer formed on one side of an acrylic foam layer having a predetermined thickness, a base layer formed on one side of both sides of the acrylic foam layer, a pressure- The present invention also provides a double-faced acrylic foam tape having a substrate layer, which is constituted by a releasing paper to be formed.
However, in the case of the base layer based on the conventional acrylic foam layer including the above-mentioned prior art documents, it has not been able to meet the requirements of the related art in terms of shock absorbing property, anti-rebound property, and gap adhesion with the adherend. In addition, when the tape including the conventional base layer is placed at a low temperature or a high temperature, the physical properties of the tape may be lowered, and the tape can not cope with the diversified conditions. As a result, there has been a need for improvement of cold resistance, heat resistance, waterproofness, impact absorbability and durability, and studies have been actively carried out to improve these properties.
Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to provide a composition for producing a base layer, which is improved in physical properties such as cold resistance, heat resistance, durability, impact absorbability, water resistance and anti- The purpose is to provide.
The thermally expandable microspheres include an outer shell made of a thermoplastic resin and a blowing agent contained in the outer shell and having a boiling point lower than the softening point of the thermoplastic resin, The foaming agent includes one selected from the group consisting of hydrocarbons having 1 to 12 carbon atoms, halides of hydrocarbons having 1 to 12 carbon atoms, and compounds capable of generating gases by pyrolysis by heating, wherein the thermally expandable microspheres are heated And the resulting mixture is foamed. The present invention can be achieved by providing a composition for producing a base layer.
According to another preferred feature of the present invention, the thermally expandable microspheres may be contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the binder resin.
According to another preferred feature of the present invention, it is possible to further include a crosslinking agent.
According to another preferred feature of the present invention, it may further comprise a colorant.
According to another preferred feature of the present invention, the binder resin is at least one selected from the group consisting of methyl (meth) acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate .
According to another preferred feature of the present invention, the thermally expandable microspheres can be foamed at 100 to 170 占 폚.
According to another preferred feature of the present invention, the expansion ratio of the thermally expandable microspheres may be 2 to 20 times the magnetic volume.
According to another preferred feature of the present invention, the thermally expandable microspheres may have an average particle diameter of 5 to 50 mu m.
According to another preferred feature of the present invention, the density of the thermally expandable microspheres can be reduced by heating.
According to the composition for preparing a substrate layer according to the present invention, it is possible to improve the physical properties such as cold resistance, heat resistance, durability, impact absorbability, water resistance and anti-repulsion property by including thermally expandable microspheres, .
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It is to be understood, however, that the embodiments described below are only for explanation of the embodiments of the present invention so that those skilled in the art can easily carry out the invention, It does not mean anything.
The present invention relates to a composition for producing a base layer. Hereinafter, the composition for preparing a base layer according to the present invention will be described in detail.
The composition for preparing a base layer according to the present invention may include a binder resin and a thermally expandable microspheres.
The binder resin is a copolymer resin polymerized with an acrylic monomer and at least one selected from the group consisting of methyl (meth) acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate is polymerized . ≪ / RTI >
And may be obtained by polymerizing at least one monomer selected from a monomer having a hydroxyl group, a monomer having an amide group, a monomer having a tertiary amine group, and a monomer having a carboxyl group. At this time, the monomer may be mixed so as to include 0.1 to 50 wt%, preferably 1 to 20 wt%, based on the total composition.
Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-deoxybutyl (meth) acrylate, 4-hydroxybutyl Acrylate, 2-hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group, (Meth) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, Nonyl vinyl ether, 10-hydroxydecyl vinyl ether, and the like.
Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.
Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) ) Acrylate, and the like.
As the monomer having a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and the like are preferable.
The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control and the like which are usually used in polymerization can be used.
In the present invention, the thermally expandable microspheres have a structure in which the thermoplastic resin is outer shell and the foaming agent is enclosed therein. Specifically, the thermally expandable microspheres have a closed-cell shape.
The thermoplastic resin includes at least one selected from a nitrile monomer, a carboxyl group-containing monomer, vinylidene chloride, vinyl acetate, a (meth) acrylic acid ester monomer, a styrene monomer, an acrylamide monomer and a maleimide monomer , And preferably one obtained by polymerization from a nitrile-based monomer.
The foaming agent is contained in the outer shell and has a boiling point of not higher than the softening point of the thermoplastic resin and is characterized by being able to improve impact resistance, anti-repulsion property, adhesion agent and gap adhesion property of the base layer composition as it is foamed upon heating.
The foaming agent may include one selected from the group consisting of hydrocarbons having 1 to 12 carbon atoms, halides of hydrocarbons having 1 to 12 carbon atoms, and compounds capable of pyrolyzing by heating to produce a gas.
Specifically, the hydrocarbon having 1 to 12 carbon atoms is preferably selected from the group consisting of propane, cyclopropane, propylene, normal butane, isobutane, cyclobutane, normal pentane, cyclopentane, isopentane, neopentane, normal hexane, isohexane, cyclohexane, Cycloheptane, octane, isooctane, cyclooctane, 2-methylpentane, 2,2-dimethylbutane, petroleum ether and the like.
Halides of hydrocarbons having 1 to 12 carbon atoms include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, and the like.
Examples of the compound which pyrolyzes by heating to generate a gas include azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, 4,4'-oxybis (benzenesulfonylhydride) and the like.
The thermally expandable microspheres can be foamed by heating. The thermally expandable microspheres can be foamed at the foaming temperature. The foaming temperature of the thermally expandable microspheres may be 100-170 캜, preferably 100-150 캜. That is, the thermally expandable microspheres can be foamed at 100 to 170 占 폚, preferably at 100 to 150 占 폚.
The present invention improves physical properties such as adhesion force by causing foaming of thermally expandable microspheres by heating to a specific temperature in a composition for preparing a base layer containing thermally expandable microspheres and a binder resin before foaming.
The density of the thermally expandable microspheres can be reduced by heating, and the density of the heat-expandable microspheres after heating can be reduced by about 0.01 to 0.5 g / cm 3 compared to before heating.
The expansion ratio of the thermally expanding microspheres may be from 2 to 50, preferably from 2 to 20, based on the magnetic volume.
The particle size of the thermally expandable microspheres may be 1 to 100 탆, preferably 5 to 50 탆.
The thermally expandable microspheres may be mixed in an amount of 1 to 15 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the binder resin. When the thermally expandable microspheres are mixed according to the above-mentioned criteria and are included in the composition for preparing a base layer, they exert more excellent effects in terms of adhesion, heat resistance and cold resistance.
The composition for preparing a base layer according to the present invention may further comprise a crosslinking agent. The crosslinking agent is a component for imparting durability by reinforcing the cohesive strength or the adhesive strength of the composition for the base layer formation by chemical bonding. The crosslinking agent may include an isocyanate compound, an epoxy compound, and the like, and these may be used alone or in combination of two or more. The isocyanate-based compound and the like are included so that the heat resistance can be improved.
Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate , Diisocyanate compounds such as naphthalene diisocyanate; An adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate compound in which 3 moles of a diisocyanate compound is self-condensed, a diisocyanate obtained from 2 moles of 3 moles of a diisocyanate compound And multifunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate in which the remaining one mole of diisocyanate is condensed in urea.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether, glycerol diglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N ', N'-tetraglycidyl-m-glycidoxyethyl isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.
In addition, an isocyanate compound, an epoxy compound, and a melamine compound may be used alone or in admixture of two or more. Examples of the melamine-based compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.
The crosslinking agent may be contained in an amount of 0.1 to 10 wt%, preferably 0.3 to 3 wt%, based on the total composition.
The composition for preparing a base layer according to the present invention may further comprise a coloring agent. The colorant is a component to be added for the shading effect and is not particularly limited to the color of the colorant, but may preferably be a black colorant.
As the black colorant, a black pigment or a black dye can be used. As the black pigment, organic pigments or inorganic pigments generally used in the art can be used. As the pigment, various pigments used for printing ink, ink-jet ink and the like can be used, and examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. The black dye can be used without limitation as long as it has solubility in an organic solvent.
In addition to the above-described components, the composition for preparing a substrate layer according to the present invention may contain additives such as fillers, antistatic agents, antioxidants, and silane coupling agents in order to control the adhesion, cohesion, viscosity, .
Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.
Production Example 1. Synthesis of binder resin
45 parts by weight of n-butyl acrylate (BA), 45 parts by weight of 2-ethylhexyl acrylate, and 10 parts by weight of acrylic acid were added to a 1 L reactor equipped with a cooling device for regulating the temperature of the nitrogen gas, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 80 ° C. After the mixture was homogenized, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 6 hours to prepare an acrylic binder resin.
Production Example 2. Preparation of black colorant
12 parts by weight of C.I. Pigment Black 1 and 4.0 parts by weight of BYK-2001 as a pigment dispersant were mixed in an organic solvent and the pigment was sufficiently dispersed using a bead mill to prepare a black colorant.
Example 1
(1) Composition for producing a base layer
On the basis of the solid content, 100 parts by weight of the acrylic copolymer of Production Example 1, 5 parts by weight of F-50D (average particle diameter: 15 mu m) as thermally expandable microspheres and 10 parts by weight of other additives were mixed, And then diluted with an organic solvent to prepare a composition for preparing a base layer.
(2)
The base layer composition prepared in the above step (1) was allowed to stand at room temperature for about 30 minutes to remove bubbles, and was then applied onto a PET film (50um, corresponding to the substrate) and dried under the conditions shown in Table 1 The thermally expandable microspheres were foamed) to form a base layer. And another layer of a release film was laminated thereon.
In Table 1, the foaming rate was calculated according to the following equation (1).
&Quot; (1) "
(15 占 퐉) of the thermally expandable microspheres (15 占 퐉) of the thermally expandable microspheres;
As shown in Table 1, the thermally expandable microspheres (F-50D) started foaming at about 100 ° C. and reached maximum foaming at about 145 ° C., and from about 150 ° C. or higher, the foaming rate Respectively.
Example 2. Impact resistance test
The composition prepared in Example 1 (1) was allowed to stand at room temperature for about 30 minutes to remove air bubbles and then applied on a PET film (50um), and dried under the conditions shown in Table 1 (heat- The microspheres were foamed) to form a base layer. At this time, the thickness of the base layer including the PET film was 120 mu m.
An acrylic pressure-sensitive adhesive was coated on both sides of the base layer to form a pressure-sensitive adhesive layer, and then left at 60 DEG C for 2 days. The laminate was cut into a size of 15.5 mm X 15.5 mm and adhered to PC and glass adhered to both sides with a force of 5 kg / 5 sec. The sample was left standing at room temperature for 72 hours.
The weight of the specimen was dropped from 50 mm to 500 mm at an interval of 50 mm while the weight was dropped. The weights were measured while increasing the weight from 50 g to 10 g or 50 g, and the average value was calculated by repeating this experiment three times. The results are shown in Table 2 below.
As a control, a pressure-sensitive adhesive layer was formed on both sides of a (PE foam, 120 μm thickness) acrylic adhesive, and the same test was conducted after standing at 60 ° C. for 2 days.
As shown in Table 2 above, it was shown that the specimen including the substrate layer including the thermally expandable microspheres was able to withstand a stronger impact than the control. This indicates that the thermoexpandable microspheres contained in the composition play a role in relieving the impact.
Example 3: Impact resistance test according to the content of thermally expandable microspheres
As shown in the following Table 3, the composition for preparing the base layer was prepared by varying the content (unit: parts by weight) of thermally expandable microspheres, and the impact resistance test was carried out in the same manner as in Example 2.
As shown in Table 3, when the thermally expandable microspheres were contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the acrylic copolymer, excellent impact resistance was exhibited.
Claims (9)
Wherein the thermally expandable microspheres comprise an outer periphery made of a thermoplastic resin and a foaming agent contained in the outer periphery and having a boiling point lower than the softening point of the thermoplastic resin,
The foaming agent includes one selected from the group consisting of a hydrocarbon having 1 to 12 carbon atoms, a halide of a hydrocarbon having 1 to 12 carbon atoms, and a compound generating pyrolysis by heating to produce a gas,
The thermally expandable microspheres are foamed by heating,
The heating temperature of the thermally expandable microspheres is 130 to 160 DEG C,
Wherein the thermally expandable microspheres are contained in an amount of 5 to 10 parts by weight based on 100 parts by weight of the binder resin.
Wherein the composition for preparing a base layer further comprises a crosslinking agent.
Wherein the composition for preparing a base layer further comprises a coloring agent.
Wherein the binder resin is obtained by polymerizing at least one member selected from the group consisting of methyl (meth) acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate. Composition.
Wherein the expansion ratio of the thermally expandable microspheres is 2 to 20 relative to the magnetic volume.
Wherein the thermally expandable microspheres have an average particle diameter of 5 to 50 占 퐉.
Wherein the heat-expandable microspheres have a reduced density by heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160002808A KR101775652B1 (en) | 2016-01-08 | 2016-01-08 | Composition for substrate layer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160002808A KR101775652B1 (en) | 2016-01-08 | 2016-01-08 | Composition for substrate layer |
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| Publication Number | Publication Date |
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| KR20170094467A KR20170094467A (en) | 2017-08-18 |
| KR101775652B1 true KR101775652B1 (en) | 2017-09-27 |
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| KR1020160002808A KR101775652B1 (en) | 2016-01-08 | 2016-01-08 | Composition for substrate layer |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003238908A (en) * | 2002-02-14 | 2003-08-27 | Nitto Denko Corp | Pressure sensitive adhesive sheet |
| JP5759640B1 (en) * | 2013-10-24 | 2015-08-05 | 松本油脂製薬株式会社 | Thermally expansible microspheres, production method and use thereof |
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2016
- 2016-01-08 KR KR1020160002808A patent/KR101775652B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003238908A (en) * | 2002-02-14 | 2003-08-27 | Nitto Denko Corp | Pressure sensitive adhesive sheet |
| JP5759640B1 (en) * | 2013-10-24 | 2015-08-05 | 松本油脂製薬株式会社 | Thermally expansible microspheres, production method and use thereof |
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| KR20170094467A (en) | 2017-08-18 |
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