CN101586006A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and method for producing the same - Google Patents

Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and method for producing the same Download PDF

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CN101586006A
CN101586006A CNA2009102029569A CN200910202956A CN101586006A CN 101586006 A CN101586006 A CN 101586006A CN A2009102029569 A CNA2009102029569 A CN A2009102029569A CN 200910202956 A CN200910202956 A CN 200910202956A CN 101586006 A CN101586006 A CN 101586006A
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monomer
pressure sensitive
methyl
monomer mixture
composition
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丹羽理仁
冈本昌之
樋口真觉
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Nitto Denko Corp
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Abstract

The present invention relates to a pressure-sensitive adhesive composition including, as a main ingredient, a monomer mixture or an acrylic copolymer material obtained by at least partially polymerizing the monomer mixture, the monomer mixture including: at least one monomer (monomer ml) selected from alkyl (meth)acrylates represented by the following formula (I) CH2-C(R1)COOR2 in which R1 is a hydrogen atom or a methyl group, and R2 is an alkyl group having 1 to 20 carbon atoms: at least one monomer (monomer m2) selected from N-hydroxyalkyl (meth)acrylamides represented by the following formula (II) CH2-C(R1)CONHR4 in which R3 is a hydrogen atom or a methyl group, and R4 is a hydroxyalkyl group having 2 to 4 carbon atoms: and at least one monomer (monomer m3) selected from N-vinyl cyclic amides and (meth)acrylamides that may have an N-alkyl group; and the monomer mixture including substantially no carboxyl group-containing monomer.

Description

Contact adhesive composition, pressure sensitive adhesion sheet and production method thereof
Technical field
The present invention relates to pressure sensitive adhesive and (hereinafter be also referred to as tackiness agent, and this will be used for hereinafter) composition and pressure sensitive adhesion sheet, and especially, the present invention relates to be applicable to the application that directly is bonded in the metallic surface or the pressure sensitive adhesion sheet of other various application, and relate to a kind of contact adhesive composition that is used for this pressure sensitive adhesion sheet.The invention further relates to a kind of method of producing this pressure sensitive adhesion sheet.
Background technology
In recent years, pressure sensitive adhesion sheet has been used for all respects for example fixing (bonding), transportation, protection, the decoration etc. of goods.The representative instance of pressure sensitive adhesion sheet comprises and being provided with by using those of pressure sensitive adhesive layer that acrylic pressure-sensitive adhesive compositions forms.This acrylic pressure-sensitive adhesive compositions constitutes like this: make it to form and contain the pressure sensitive adhesive layer of acrylic copolymer as matrix polymer.In order to improve the purpose of bond properties etc.,, use usually to comprise alkyl (methyl) acrylate as main component (main ingredient) and further comprise those that comprise that for example acrylic acid copolymerization of carboxylic monomer is formed as acrylic copolymer.
Yet, (for example has product with metallic surface for the goods that are used to have the parts of forming by the material that is subjected to the acid influence easily, electronic unit for example) pressure sensitive adhesion sheet, when it has aforesaidly when comprising that carboxylic monomeric copolymerization is formed, the carboxyl in the acrylic copolymer may be the reason that above-mentioned materials is caused disadvantageous effect (for example corrosion).Therefore, be used to form and be arranged on the contact adhesive composition that is used for the pressure sensitive adhesive layer in these pressure sensitive adhesion sheets of using (especially for the application that directly is bonded on the metallic surface), preferably make it possible to form have and do not comprise acrylic copolymer that carboxylic monomeric copolymerization forms structure as the pressure sensitive adhesive layer of matrix polymer.As about this class technique background technical literature, can exemplify JP-A-2007-63536, JP-A-2005-325250 and JP-A-2007-264092.Background technology document as about acrylic adhesives can exemplify JP-A-2007-264092.JP-A-2003-165965 is the background technology document about pressure sensitive adhesive and tackiness agent.
Yet, do not comprise that carboxylic monomeric contact adhesive composition is tending towards having the insufficient adhesion characteristic of the pressure sensitive adhesion sheet that is formed by said composition.In this; JP-A-2007-63536 has described and specific maleimide compounds copolymerization; JP-A-2005-325250 has described for example N-acryloyl morpholine copolymerization of monomer with nitrogen atom, and JP-A-2000-303045 described the use specific monomer for example the vinylformic acid phenoxy ethyl as the principal monomer component.Yet, even in by the pressure sensitive adhesion sheet that uses these technology formation, the space of improving bond properties is arranged also.For example, usefully provide a kind of and do not using the contact adhesive composition that shows desirable force of cohesion under the carboxylic monomer situation and further can form the pressure sensitive adhesion sheet of anti-repellency (repellingresistance) (binding property on the curved surface) with increase.
Summary of the invention
Made the present invention according to conventional situation, and an object of the present invention is to provide at the acrylic pressure-sensitive adhesive compositions that does not use the pressure sensitive adhesion sheet that can form bond properties (particularly anti-repellency) under the situation that contains carboxylic monomer substantially with raising.Another object of the present invention provides the pressure sensitive adhesion sheet that uses this contact adhesive composition.Another purpose of the present invention provides the method for producing pressure sensitive adhesion sheet.
That is, the present invention relates to following project (1)-(8).
(1) a kind of contact adhesive composition, it comprise monomer mixture or by with the partially polymerized at least acrylic copolymer material that obtains of monomer mixture as main component,
This monomer mixture comprises:
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m1) that is selected from by alkyl (methyl) acrylate of following formula (I) expression of 50-85wt%:
CH 2＝C(R 1)COOR 2 (I)
R wherein 1Be hydrogen atom or methyl, and R 2For having the alkyl of 1-20 carbon atom,
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m2) that is selected from by N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression of 0.1-12wt%:
CH 2＝C(R 3)CONHR 4 (II)
R wherein 3Be hydrogen atom or methyl, and R 4For hydroxyalkyl with 2-4 carbon atom and
Based on the total amount of monomer mixture, its amount is at least a N-of the being selected from vinyl cyclic amide and the monomer (monomer m3) that can have (methyl) acrylamide of N-alkyl of 10-40wt%; And
This monomer mixture does not comprise carboxylic monomer substantially.
(2) according to (1) described composition, wherein, comprise monomer m1, monomer m2 and monomer m3 with the total amount more than the 90wt% based on the total amount of monomer mixture.
(3) according to (1) or (2) described composition, wherein this monomer mixture has the feasible monomer composition that has the second-order transition temperature (Tg) below-10 ℃ by the acrylic copolymer that the monomer mixture polymerization is obtained.
(4) according to each described composition of (1)-(3), wherein monomer m2 is N-(2-hydroxyethyl) (methyl) acrylamide.
(5) according to each described composition of (1)-(4), wherein monomer m3 is at least a monomer that is selected from by the N-vinyl cyclic amide of following formula (III) expression:
Figure A20091020295600061
R wherein 5It is divalent organic group.
(6) according to each described composition of (1)-(5), it is used for directly being bonded in the pressure sensitive adhesion sheet of metallic surface.
(7) a kind of pressure sensitive adhesion sheet, it comprises the pressure sensitive adhesive layer that forms according to each described composition of (1)-(6) by using.
(8) a kind of method of producing pressure sensitive adhesion sheet, described method comprises:
Production comprises monomer mixture or by being the contact adhesive composition of 0.01-2 weight part Photoepolymerizationinitiater initiater with the partially polymerized acrylic copolymer material that obtains of monomer mixture with based on 100 weight parts monomers mixtures,
This monomer mixture comprises:
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m1) that is selected from by alkyl (methyl) acrylate of following formula (I) expression of 50-85wt%:
CH 2＝C(R 1)COOR 2 (I)
R wherein 1Be hydrogen atom or methyl, and R 2For having the alkyl of 1-20 carbon atom,
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m2) that is selected from by N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression of 0.1-12wt%:
CH 2＝C(R 3)CONHR 4 (II)
R wherein 3Be hydrogen atom or methyl, and R 4For hydroxyalkyl with 2-4 carbon atom and
Based on the total amount of monomer mixture, its amount is at least a N-of the being selected from vinyl cyclic amide and the monomer (monomer m3) that can have (methyl) acrylamide of N-alkyl of 10-40wt%, and
This monomer mixture does not comprise carboxylic monomer substantially;
This contact adhesive composition is applied on the supporting mass; With
By the composition that applies with rayed this composition that applies is solidified, form pressure sensitive adhesive layer thus.
Being somebody's turn to do " acrylic copolymer material " can be the partially polymerized product of monomer mixture, perhaps the acrylic copolymer that obtains by most monomer mixture polymerization (for example about more than 95%, preferred about transformation efficiency more than 99%).The partially polymerized product of monomer mixture can comprise that usually (it can comprise the monomer with low relatively polymerization degree, and for example it can comprise having and is no more than 1 * 10 usually for the polymkeric substance that obtains by the monomer polymerization with the compositing monomer mixture of part ratio 4The polymkeric substance (it also can be called as oligopolymer) of weight-average molecular weight) and unconverted monomer.The transformation efficiency of this partially polymerized product (promptly in the monomer that uses the monomeric ratio of polymeric) in advance can be for example about 2-50%.In addition, contact adhesive composition disclosed herein comprises that monomer mixture or acrylic copolymer material are meant that as the statement of main component acrylic copolymer by the monomer mixture polymerization is obtained (it can be the polymkeric substance that obtains by polymerization or the curing by irradiates light of monomer mixture or its partially polymerized product etc., perhaps is acrylic copolymer material itself substantially) constitutes pressure sensitive adhesive with this contact adhesive composition formation as matrix polymer (main ingredient in the polymeric constituent).
Because this contact adhesive composition comprises the monomer mixture that do not use the monomer (carboxylic monomer) that contains carboxyl substantially or acrylic copolymer material as main component, therefore, can prevent that also metallic surface etc. from being corroded by carboxyl even when will directly being bonded in the surface formed by the material that is subjected to acid easily and influences by the pressure sensitive adhesive layer that uses said composition to form for example during the metallic surface.In addition, have by use and to comprise that acrylic copolymer that monomer m1 forms (as each monomeric ratio of monomer component) as the monomer of the monomer m2 of main ingredient and predetermined amount and monomer m3 is as main component, can form the pressure sensitive adhesive layer (be the pressure sensitive adhesion sheet that comprises pressure sensitive adhesive layer therefore perhaps, and this will be used for hereinafter) that has high cohesion and show the anti-repellency of further raising.
As the preferred embodiment of monomer m2, can mention N-(2-hydroxyethyl) (methyl) acrylamide.Wherein, preferably use N-(2-hydroxyethyl) acrylamide.As monomer m3, can preferably use at least a monomer that is selected from by the N-vinyl cyclic amide of following formula (III) expression in addition:
Figure A20091020295600081
R wherein 5It is divalent organic group.
As the preferred embodiment of N-vinyl cyclic amide, can mention that N-vinyl-2-Pyrrolidone (is the R in its Chinese style (III) 5Be the compound of propylidene).
Here in the preferred embodiment of disclosed contact adhesive composition, based on the total amount of monomer mixture, the total amount of monomer m1, m2 and m3 is about more than the 90wt%.Comprise the monomer mixture of this composition or acrylic copolymer material and can form pressure sensitive adhesive layer with better quality stability as the contact adhesive composition of main component.
This monomer mixture preferably has such monomer and forms: make to have the second-order transition temperature (Tg) of (common-10 to-70 ℃ approximately) below-10 ℃ approximately by the acrylic copolymer (i.e. matrix polymer in the pressure sensitive adhesive that forms with contact adhesive composition) that the monomer mixture polymerization is obtained.This binder composition can form the pressure sensitive adhesive layer of the bond properties (tackiness etc.) that for example shows under normal temperature (about usually 5-35 ℃, for example 20-25 ℃).
In this article in another preferred embodiment of disclosed contact adhesive composition, said composition comprises Photoepolymerizationinitiater initiater, and by can solidified contact adhesive composition (photo curable contact adhesive composition) is formed by light (for example ultraviolet ray) irradiation.For example, it can be the contact adhesive composition that forms for about 0.01-2 weight part Photoepolymerizationinitiater initiater based on 100 weight parts monomers mixtures by using.Go up the pressure sensitive adhesive layer that forms and to show better bond properties (for example force of cohesion, anti-repellency etc.) by light shining this photo curable contact adhesive composition (it can be called as the contact adhesive composition etc. of photopolymerization).
According to the present invention, provide comprise a kind of comprising by acrylic copolymer that any monomer mixture polymerization disclosed herein is obtained pressure sensitive adhesion sheet as the pressure sensitive adhesive layer of matrix polymer.This pressure sensitive adhesive layer can be the pressure sensitive adhesive layer by using any contact adhesive composition disclosed herein to form.That is to say,, provide the pressure sensitive adhesion sheet that comprises by the pressure sensitive adhesive layer that uses any contact adhesive composition formation disclosed herein according to the present invention.Because this pressure sensitive adhesion sheet comprises the polymkeric substance that stems from monomer mixture or acrylic copolymer material as matrix polymer, therefore even when it directly being bonded in the surface formed by the material that is subjected to acid easily and influences for example during the metallic surface, do not have corrosion etc. yet.Therefore, it is suitable as the pressure sensitive adhesion sheet (will be bonded in the pressure sensitive adhesion sheet of metallic surface) that is used for directly being bonded on the metallic surface.In addition, the binding property that this pressure sensitive adhesion sheet can show on the agglutinating object treating except the metallic surface, and good force of cohesion and anti-repellency.In addition, any contact adhesive composition disclosed herein is suitable as the contact adhesive composition of the pressure sensitive adhesive layer that is used to form the pressure sensitive adhesion sheet that will be bonded in the metallic surface.
According to the present invention, also provide the method that on the metallic surface, prepares pressure sensitive adhesion sheet (it can be the pressure sensitive adhesion sheet that will be bonded in the metallic surface).This method comprises that preparation comprises the monomer mixture that satisfies all following conditions (a)-(d), perhaps the step of the contact adhesive composition by the partially polymerized acrylic copolymer material that obtains of this monomer mixture.In preferred embodiments, use in this step based on 100 weight parts monomers mixtures, its amount is the Photoepolymerizationinitiater initiater of about 0.01-2 weight part.
(a) this monomer mixture comprises at least a monomer (monomer m1) that is selected from by alkyl (methyl) acrylate of following formula (I) expression.Based on the total amount of monomer mixture, the content of monomer m1 can be 50-85wt%:
CH 2＝C(R 1)COOR 2 (I)
R wherein 1Be hydrogen atom or methyl, and R 2For having the alkyl of 1-20 carbon atom.
(b) this monomer mixture comprises at least a monomer (monomer m2) that is selected from by N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression.Based on the total amount of monomer mixture, the content of monomer m2 can be 0.1-12wt%:
CH 2＝C(R 3)CONHR 4 (II)
R wherein 3Be hydrogen atom or methyl, and R 4For having the hydroxyalkyl of 2-4 carbon atom.
(c) this monomer mixture comprises at least a N-of being selected from vinyl cyclic amide and the monomer (monomer m3) that can have (methyl) acrylamide of N-alkyl.Based on total monomer mixture, the content of monomer m3 can be 10-40wt%.
(d) this monomer mixture does not comprise carboxylic monomer substantially.
The method that is used to produce pressure sensitive adhesion sheet further comprises contact adhesive composition is applied in the step on the supporting mass and makes composition solidify, form thus the step of pressure sensitive adhesive layer on the composition that applies by light shining.
By this method, can prepare for example metallic surface and further have the pressure sensitive adhesion sheet of good bond properties (force of cohesion, anti-repellency etc.), the surface of can be preferably even being used for being subjected to easily the acid influence effectively.In addition, be preferred for producing the method that wherein forms the pressure sensitive adhesion sheet of pressure sensitive adhesive layer, because it can easily form thick binder layer by the aforesaid Photocurable adhesive composition of use.
Description of drawings
Fig. 1 is the schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Fig. 2 is another schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Fig. 3 is the another schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Fig. 4 is another schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Fig. 5 is the another schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Fig. 6 is the another schematic cross section that illustrates according to the structure example of pressure sensitive adhesion sheet of the present invention.
Reference number and description of reference numerals
1: base material
2: pressure sensitive adhesive layer
3: barrier liner
11,12,13,14,15 and 16: pressure sensitive adhesion sheet
Embodiment
Suitable embodiment of the present invention hereinafter will be described.In addition, by the design of those skilled in the art, can figure out the enforcement key element required for the present invention except the key element of specifically mentioning in this manual based on the background technology of association area.The present invention can implement according to disclosed content in the ordinary skill knowledge in the association area and this specification sheets.
Contact adhesive composition disclosed herein have predetermined monomer mixture or by the partially polymerized acrylic copolymer material that obtains of monomer mixture as main component.This monomer mixture comprises that at least monomer m1, monomer m2 and monomer m3 are as necessary component.
Monomer m1 is the component as the principal monomer (main ingredient) that constitutes monomer mixture, and comprises alkyl (methyl) acrylate by following formula (I) expression, i.e. (methyl) acrylate of alkyl alcohol.Here, " (methyl) vinylformic acid " means and comprises vinylformic acid and methacrylic acid.In addition, monomer m1 is that the statement of principal monomer is meant the total amount based on monomer mixture, and the amount of monomer m1 (comprising that under two or more situations by alkyl (methyl) acrylate of formula (I) expression be its total amount) is for more than the 50wt%.
Monomer m1 is selected from by one or more of alkyl (methyl) acrylate of following formula (I) expression.
CH 2＝C(R 1)COOR 2 (I)
Here, the R in the formula (I) 1Be hydrogen atom or methyl.In addition, the R in the formula (I) 2For having the alkyl of 1-20 carbon atom.This alkyl can be linearity or branching.Specific examples by alkyl (methyl) acrylate of formula (I) expression comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinylformic acid heptadecane ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid nonadecane ester and (methyl) vinylformic acid eicosane ester.Wherein, preferred R wherein 2(this carbon atom scope can be called as " C hereinafter for alkyl with 2-14 carbon atom 2-14") alkyl (methyl) acrylate, and more preferably R wherein 2Be C 2-10Alkyl (methyl) acrylate of alkyl (for example normal-butyl, 2-ethylhexyl etc.).
In preferred embodiments, the R in its Chinese style (1) 2Be C 2-10(more preferably C 4-8) alkyl (methyl) acrylate of alkyl accounts for about 70wt% above (more preferably from about more than the 90wt%) of monomer m1 total amount.Basic all monomer m1 can be C 2-10Alkyl (more preferably C 4-8Alkyl) (methyl) acrylate.This monomer mixture can be for example comprise separately butyl acrylate (BA) as the composition of monomer m1, separately comprise 2-EHA (2EHA) as the composition of monomer m1, comprise these the two kinds compositions that are BA and 2EHA as monomer m1.
Based on the total amount of monomer mixture, the amount of monomer m1 can be about 50-85wt% (preferred 60-80wt%).When the amount of monomer m1 was lower than above-mentioned scope, the pressure sensitive adhesive layer that is formed by said composition had the trend of insufficient bond properties (binding property, tackiness etc.).On the other hand, when the amount of monomer m1 is higher than above-mentioned scope, because the amount of monomer m2 in the monomer mixture and monomer m3 that is contained in reduces, so the possible deterioration of consistency between force of cohesion (for example the weather resistance to peeling off under certain stress, it is a kind of static load characteristic) and the anti-repellency.In addition, the common copolymerization ratio of the composition of monomer mixture (monomer composition) corresponding to the acrylic copolymer that obtains by the monomer mixture polymerization (i.e. matrix polymer in the pressure sensitive adhesive that forms by contact adhesive composition disclosed herein).
Except the monomer m1 as principal monomer, this monomer mixture further comprises monomer m2.This monomer m2 is selected from by one or more of N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression.
CH 2＝C(R 3)CONHR 4 (II)
Here, the R in the formula (II) 3Be hydrogen atom or methyl.In addition, the R in the formula (II) 4For having the hydroxyalkyl of 2-4 carbon atom.Alkyl in the hydroxyalkyl can be linearity or branching.Specific examples by N-hydroxyalkyl (methyl) acrylamide of formula (II) expression comprises N-(2-hydroxyethyl) acrylamide, N-(2-hydroxyethyl) Methacrylamide, N-(2-hydroxypropyl) acrylamide, N-(2-hydroxypropyl) Methacrylamide, N-(1-hydroxypropyl) acrylamide, N-(1-hydroxypropyl) Methacrylamide, N-(3-hydroxypropyl) acrylamide, N-(3-hydroxypropyl) Methacrylamide, N-(2-hydroxyl butyl) acrylamide, N-(2-hydroxyl butyl) Methacrylamide, N-(3-hydroxyl butyl) acrylamide, N-(3-hydroxyl butyl) Methacrylamide, N-(4-hydroxyl butyl) acrylamide and N-(4-hydroxyl butyl) Methacrylamide.From forming the pressure sensitive adhesive layer viewpoint that has in balance good between wetting ability and the hydrophobic nature and the excellent balance between the pressure sensitive adhesion performance, the example of the monomer m2 among preferred the present invention comprises N-(2-hydroxyethyl) acrylamide and N-(2-hydroxyethyl) Methacrylamide.Especially, preferably use N-(2-hydroxyethyl) acrylamide (HEAA).For example, the monomer m2 of 50wt% above (more preferably more than the 70wt%, whole substantially usually) is preferably HEAA.
Because the interaction between the monomer m2 molecule, so monomer m2 can play and helps to improve pressure sensitive adhesive accumulative component.Based on the total amount of monomer mixture, the amount of monomer m2 can be about 0.1-12wt% (about usually 1-10wt%).When the amount of monomer m2 was lower than above-mentioned scope, the pressure sensitive adhesive layer that is formed by said composition had the trend of insufficient bond properties (binding property under the high temperature, under certain stress to the weather resistance peeled off etc.).On the other hand, when the amount of monomer m2 is higher than above-mentioned scope, the trend that exists tackiness at a lower temperature or binding property to reduce.
In this article in the preferred embodiment of disclosed contact adhesive composition, total amount based on monomer mixture, the amount of monomer m2 is about 2wt% above (2-12wt% usually), and more preferably from about more than the 3wt% (about usually 3-12wt%, for example about 3-10wt%).By this binder composition, can obtain to form the effect of pressure sensitive adhesion sheet with better force of cohesion and anti-repellency.
The weight ratio (m1/m2) of monomer m1 and monomer m2 can be for example about 99/1-80/20 in this monomer mixture.Usually, this weight ratio is preferably about 98/2-85/15 (more preferably from about 97/3-90/10).By this binder composition, can obtain to form the effect of pressure sensitive adhesion sheet with better force of cohesion and anti-repellency.Based on the total amount of monomer mixture, the total amount of monomer m1 and monomer m2 can be for example about 60-90wt%.Based on the total amount of monomer mixture, its total amount is preferably about 70wt% above (for example 70-90wt%).
Except monomer m1 and m2, this monomer mixture further comprises monomer m3.This monomer m3 can be at least a monomer that is selected from the group of being made up of N-vinyl cyclic amide and (methyl) acrylamide that can have the N-alkyl.The specific examples of N-vinyl cyclic amide comprises N-vinyl-2-Pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholone mai, N-vinyl-2-hexanolactam, N-vinyl-1,3-oxazine (oxadine)-2-ketone and N-vinyl-3, the 5-morpholine diketone.The specific examples that can have (methyl) acrylamide of N-alkyl comprises for example N-alkyl (methyl) acrylamide of (methyl) acrylamide; N-ethyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide; And N, N-dialkyl group (methyl) acrylamide is N for example, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-two (normal-butyl) (methyl) acrylamide, N, N-two (tertiary butyl) (methyl) acrylamide.The preferred use contained one or two (methyl) acrylamide with N-alkyl of 1-4 carbon atom (more preferably 1 or 2 carbon atom) (for example N, N-dialkyl group acrylamide such as N, N-diethyl acrylamide, N,N-DMAA).
As the monomer m3 in the technology disclosed herein, can preferably use N-vinyl cyclic amide by following formula (III) expression:
R wherein 5It is divalent organic group.R in the following formula 5Preferably saturated or undersaturated alkyl, more preferably saturated hydrocarbyl (alkylidene group that for example has 3-5 carbon atom).By having the monomer mixture of this composition, can obtain to be used to form the contact adhesive composition that between adhesion characteristic, has good equilibrated pressure sensitive adhesive layer.In the present invention, exemplify N-vinyl-2-Pyrrolidone as particularly preferred N-vinyl cyclic amide.
Based on the total amount of monomer mixture, the amount of monomer m3 can be for example about 10-40wt%.When the amount of monomer m3 is higher than above-mentioned scope, the characteristic of the pressure sensitive adhesive layer that forms with said composition under low temperature environment (as the binding property of pressure sensitive adhesive etc.) may deterioration.On the other hand, when the amount of monomer m3 was lower than above-mentioned scope, force of cohesion (for example stripping strength) or anti-repellency were tending towards reducing.Be about 15-35wt% by the amount that monomer m3 is set based on the monomer mixture total amount, can realize more suitably result.
Based on the total amount of monomer mixture, the total amount of monomer m1, m2 and m3 can be for for example more than about 70wt%.Based on the total amount of monomer mixture, its total amount is preferably about 90wt% above (more preferably from about more than the 95wt%).In the preferred embodiment of disclosed contact adhesive composition, this monomer mixture is substantially only formed (promptly based on the total amount of monomer mixture, the total amount of monomer m1, m2 and m3 is 100wt% substantially) by monomer m1, m2 and m3 in this article.By this binder composition, can obtain to form the effect of pressure sensitive adhesion sheet with simple composition with good force of cohesion and anti-repellency.
With regard to technology disclosed herein, monomer mixture does not comprise carboxylic monomer substantially.Here, " carboxylic monomer " is meant the vinyl monomer (ethylenically unsaturated monomer) (it can be the form of acid anhydride) that has at least one carboxyl at an one intramolecularly.Carboxylic monomeric specific examples comprises olefinic unsaturated monocarboxylic for example (methyl) vinylformic acid and Ba Dousuan; Ethylenically unsaturated dicarboxylic is toxilic acid, methylene-succinic acid and citraconic acid for example; With ethylenically unsaturated dicarboxylic acid anhydride for example Maleic Acid, Anhydrous and anhydrous methylene-succinic acid.In addition, monomer mixture " does not comprise substantially " that carboxylic monomeric statement is meant that monomer mixture does not comprise any carboxylic monomer, and perhaps based on the total amount of monomer mixture, its amount is for below the 0.1wt%.
Preferably this monomer mixture does not comprise carboxylic monomer substantially, and this monomer mixture does not comprise the monomer that contains acidic-group (sulfonic acid group, phosphate group etc.) substantially except carboxyl.Promptly preferably this monomer except carboxylic monomer, do not comprise the monomer (this means that monomer does not comprise carboxylic monomer and the other monomer that contains acidic-group) that contains acidic-group yet, perhaps based on the total amount of monomer mixture, its total amount is below the 0.1wt%.This binder composition can form and highly prevent the corrosion pressure sensitive adhesive layer of (highly suppressing the corrosion on the metallic surface) when it is bonded on the metallic surface.
Except monomer m1 to m3, this monomer mixture can comprise other monomers (i.e. monomer except monomer m1 to m3, it can be called as " monomer m4 " hereinafter) as optional component.By using monomer m4, for example can control the various characteristics of pressure sensitive adhesive or the structure of acrylic copolymer etc. preferablyly.As monomer m4, can use be selected from can with alkyl used herein (methyl) acrylic ester copolymer and do not have carboxyl (normally carboxyl and the acidic-group except carboxyl) various monomeric one or more.For example also can use and have for example various monomers of (methyl) acryl, vinyl etc. of one or more ethylenically unsaturated groups.
The example of monomer m4 comprises monomer for example (methyl) glycidyl acrylate and the glycidyl allyl ether that contains epoxy group(ing); The monomer that contains alkoxyl group is (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid methoxyl group propyl ester, (methyl) vinylformic acid methoxyl group ethylene glycol and (methyl) vinylformic acid methoxyl group polypropylene glycol for example; The monomer of cyano-containing is vinyl cyanide and methacrylonitrile for example; Styrene monomer is vinylbenzene and alpha-methyl styrene for example; Alpha-olefin is ethene, propylene, isoprene, divinyl and iso-butylene for example; The monomer that contains isocyanate groups is 2-methacryloxyethyl isocyanic ester for example; The vinyl esters monomer is vinyl-acetic ester and propionate for example; Vinyl ethers monomer is vinyl ether for example; (methyl) acrylate that contains heterocyclic group is (methyl) tetrahydrofurfuryl acrylate for example; The monomer of halogen atom is fluorine (methyl) acrylate for example; The monomer that contains alkoxysilyl is 3-methacryloxypropyl trimethoxy silane and vinyltrimethoxy silane for example; The monomer that contains siloxane bond is silicone (methyl) acrylate for example; R in its Chinese style (I) 2Alkyl (methyl) acrylate for alkyl with the carbon atom more than 21; (methyl) acrylate that contains alicyclic alkyl is (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid norbornene ester and (methyl) isobornyl acrylate for example; With (methyl) acrylate that contains aromatic hydrocarbyl for example (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl and (methyl) vinylformic acid phenoxy group glycol ether ester.
Other examples of monomer m4 comprise the monomer of the nitrogen atom except monomer m2 and monomer m3.The example comprises ring-type (methyl) acrylamide for example N-(methyl) acryloyl morpholine and the N-acryl pyrrolidone that contains the N-acryl; Contain amino monomer for example (methyl) vinylformic acid ammonia ethyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester and (methyl) vinylformic acid N, N-dimethylamino propyl ester; The monomer that contains the maleimide main chain is N-cyclohexyl maleimide and N-phenylmaleimide for example; With clothing health acid imide monomer for example N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-2-ethylhexyl clothing health imide, N-lauryl clothing health imide and N-cyclohexyl clothing health imide.
In addition, as monomer m4, for example can use for example two (methyl) vinylformic acid glycol ester of polyfunctional monomer, two (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid hexylene glycol ester, two (methyl) vinylformic acid pentaerythritol ester, trimethylolpropane tris (methyl) acrylate, three (methyl) vinylformic acid pentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, epoxy acrylate, polyester acrylate, urethane acrylate, Vinylstyrene, two (methyl) butyl acrylates and two (methyl) Ethyl acrylate.
Other examples of monomer m4 comprise the monomer of hydroxyl, and for example (methyl) hydroxyalkyl acrylate is as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxyl ten diester and [4-(methylol) cyclohexyl] methacrylic ester; R in its Chinese style (II) 4N-hydroxyalkyl (methyl) acrylamide for hydroxyalkyl with 1 or 5 above carbon atom; With alkenyl alcohol for example vinyl alcohol and vinyl carbinol.
In addition, under the situation of monomer of using hydroxyl, from can show the viewpoint that derives from the effect of using monomer m2, the preferred monomer m4 that uses than the hydroxyl of the lower ratio of monomer m2 preferablyly as monomer m4.In other words, based on the hydroxyl monomer total amount that is contained in the monomer mixture, what preferably monomer m2 accounted for this ratio surpasses 50wt% (being generally more than the 60wt% of this ratio, more preferably more than the 75wt%, for example more than the 90wt%).As selection, the monomer that is contained in the hydroxyl in the monomer mixture can substantially only be monomer m2.
Based on the total amount of monomer mixture, the amount of monomer m4 (being its total amount comprising under two or more the situation) is suitably below about 30wt%.When the amount of monomer m4 is too high, by the balance between the pressure sensitive adhesion sheet possibility deterioration pressure sensitive adhesion performance of using said composition formation.Based on the total amount of monomer mixture, the amount of monomer m4 is preferably below about 10wt%, more preferably from about 5wt% following (for example about 2wt% is following).As selection, monomer mixture can not comprise monomer m4 (monomer mixture that promptly substantially only comprises monomer m1 to m3) substantially.
The monomer mixture that is used for technology disclosed herein preferably comprises monomer with certain proportion respectively, the Tg of the acrylic copolymer that forms by the whole approximately monomer mixture of polymerization under this ratio is about (about-10 ℃ to-70 ℃ usually) below-10 ℃, and more preferably comprise monomer with certain proportion respectively, the Tg of the acrylic copolymer that obtains by the monomer mixture polymerization under this ratio is about (about-20 ℃ to-70 ℃ usually) below-20 ℃.The composition that can regulate monomer mixture is so that Tg is in the above-mentioned scope.Here, the Tg of acrylic copolymer is meant based on the Tg of the monomeric homopolymer of compositing monomer mixture and monomeric weight fraction (copolymerization composition), by the definite value of Fox equation.The Tg value of homopolymer can obtain (" Handbook ofAdhesion Technologies " of NIKKAN KOGYO SHIMBUN, LTD., " Polymer Handbook " in Wiley-Interscience etc.) by various known materials.
The suitable embodiment of contact adhesive composition disclosed herein is to comprise monomer mixture or its partially polymerized product (the acrylic copolymer material that in other words, the comprises unconverted monomer) composition as main component.For example, it can be the contact adhesive composition that comprises the unpolymerized polymerizable functional group that stays with significant quantity (for example about 50-100mol% of monomer mixture).This class contact adhesive composition usually like this constitutes: make and go up and make polymerizable functional group reaction (polymerization) in the composition that applies with curing composition by this contact adhesive composition being applied in (it can be called as " base material ") such as the base material described after a while, barrier liners, can form pressure sensitive adhesive layer (comprising that the acrylic copolymer that obtains by the monomer mixture polymerization is as matrix polymer).Preferably avoiding carrying out the curing of contact adhesive composition with (for example at inert atmosphere for example under the nitrogen) when oxygen contacts.
Polymerization process (method that is used for curing composition) under the situation that forms pressure sensitive adhesive layer with contact adhesive composition is not particularly limited, but can use any method that is selected from the known polymerization process of various routines aptly.For example, can use the following any method that is selected from: by for example light and radioactive ray (it can be called as high-energy rays hereinafter) shine the polymerization process that carries out on the composition with active energy beam; The polymerization process (the thermopolymerization method is solution polymerization process, emulsion polymerisation process and block polymerization method for example) that the use thermal polymerization carries out etc.As the example of preferred curing, can mention the method for irradiation active energy beam (for example light, as ultraviolet ray).Contact adhesive composition disclosed herein can preferably be cured by shining this active energy beam with the composition forms that constitutes.The binder composition of this active energy beam curable (photocurable usually) is favourable, because it can easily form thick binder layer.In addition, this contact adhesive composition is fit to provide with liquid composition (non--type of solvent) form that does not contain organic solvent substantially.This viewpoint from environmental friendliness etc. is preferred.
This Photocurable adhesive composition is usually by using the Photoepolymerizationinitiater initiater preparation.For example, it can be following form: by monomer mixture and Photoepolymerizationinitiater initiater are mixed, and if desired, and the contact adhesive composition that obtains with other component blend; Mixture by comprising monomer mixture and Photoepolymerizationinitiater initiater with rayed to be forming the partially polymerized product of monomer mixture, and if desired, the contact adhesive composition that partially polymerized product and other component blend are obtained; By Photoepolymerizationinitiater initiater further being added the contact adhesive composition that obtains in (back-adding) partially polymerized product; By in the method except photopolymerization, forming the partially polymerized product of monomer mixture, and Photoepolymerizationinitiater initiater and other components are if desired added the contact adhesive composition that obtains in the partially polymerized product etc.
Photoepolymerizationinitiater initiater is not particularly limited, but can select in the various conventional known materials from the Photocurable adhesive composition field aptly.The example of Photoepolymerizationinitiater initiater comprises ketal class Photoepolymerizationinitiater initiater, acetophenones Photoepolymerizationinitiater initiater, benzoin ethers Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater, α-ketols Photoepolymerizationinitiater initiater, aromatics SULPHURYL CHLORIDE class Photoepolymerizationinitiater initiater, photolytic activity oximes Photoepolymerizationinitiater initiater, bitter almond oil camphor class Photoepolymerizationinitiater initiater, benzyl class Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater and thioxanthene ketone Photoepolymerizationinitiater initiater etc.These Photoepolymerizationinitiater initiaters can be used in combination separately or with it.
The specific examples of ketal class Photoepolymerizationinitiater initiater comprises 2,2-dimethoxy-1,2-diphenylethane-1-ketone [for example, trade(brand)name " Irgacure 651 " (being made by Ciba Japan)].The specific examples of acetophenones Photoepolymerizationinitiater initiater [for example comprises the 1-hydroxycyclohexylphenylketone, trade(brand)name " Irgacure 184 " (making) by Ciba Japan], 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 4-phenoxy group dichloroacetophenone and 4-(tertiary butyl) dichloroacetophenone.The specific examples of benzoin ethers Photoepolymerizationinitiater initiater comprises benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, benzoin iso-propylether and bitter almond oil camphor ethyl isobutyl ether.As acylphosphine oxide class Photoepolymerizationinitiater initiater, can commodity in use name " Lucirin TPO " (making) etc. by BASF.The specific examples of α-ketols Photoepolymerizationinitiater initiater comprises 2-methyl-2-hydroxypropiophenonepreparation and 1-[4-(2-hydroxyethyl) phenyl]-2-methyl-prop-1-ketone.The specific examples of aromatics SULPHURYL CHLORIDE class Photoepolymerizationinitiater initiater comprises the 2-naphthalic sulfonic chloride.The specific examples of photolytic activity oximes Photoepolymerizationinitiater initiater comprises 1-phenyl-1,1-propanedione-2-(neighbour-ethoxy carbonyl) oxime.The specific examples of bitter almond oil camphor class Photoepolymerizationinitiater initiater comprises bitter almond oil camphor.The specific examples of benzyl class Photoepolymerizationinitiater initiater comprises benzil.The specific examples of benzophenone Photoepolymerizationinitiater initiater comprises benzophenone, benzoyl phenylformic acid, 3,3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone and Alpha-hydroxy cyclohexyl-phenyl ketone.The specific examples of thioxanthene ketone Photoepolymerizationinitiater initiater comprises thioxanthone, 2-clopenthixal ketone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-di-isopropyl thioxanthone and dodecyl thioxanthone.
The amount of the Photoepolymerizationinitiater initiater that uses is not particularly limited.For example, based on 100 weight part total monomer mixtures, the amount that initiator can about 0.001-5 weight part (preferably about 0.01-2 weight part, more preferably from about 0.01-1 weight part) is used.In addition, the statement of the amount of the Photoepolymerizationinitiater initiater that will use used herein is meant the total amount of the Photoepolymerizationinitiater initiater that uses in the process that is used for preparing contact adhesive composition.Therefore, for by with behind the Photoepolymerizationinitiater initiater-join for the contact adhesive composition that obtains in the partially polymerized product that obtains by mixture with rayed monomer mixture and Photoepolymerizationinitiater initiater, it is meant and is used for the fractional total amount that partially polymerized mark and back add.
The polymerization process that is used to form the partially polymerized product of monomer mixture is not particularly limited, but can be aptly with using any method that is selected from the known polymerization process of various routines forming the identical mode of polymerization process (curing) in the pressure sensitive adhesive layer situation with contact adhesive composition.For example, can preferably use wherein with rayed by monomer mixture and Photoepolymerizationinitiater initiater and other components of using as required being mixed the light polymerization process of the mixture (preferably not containing for example mixture of organic solvent, water etc. (non--type of solvent) of liquid medium substantially) that obtains.The formation of partially polymerized product is preferably carried out with (for example for example nitrogen etc. is down at inert atmosphere) when oxygen contacts avoiding.In addition, at the polymerization process under the situation that forms partially polymerized product by monomer mixture with can be same to each other or different to each other by having polymerization process under the situation that the contact adhesive composition of partially polymerized product as main component form pressure sensitive adhesive layer (promptly using said composition to prepare polymerization process in the pressure sensitive adhesion sheet situation).
Disclosed in this article contact adhesive composition is to have in the situation of partially polymerized product as the composition (normally photo curable binder composition) of main component, the transformation efficiency of the middle monomer mixture of partially polymerized product (composition of slurries (syrup) state of preferred polymkeric substance that wherein forms by the partial monosomy polymerization of mixtures and unconverted monomer coexistence, and this partially polymerized product with this state and performance can be called as " monomer syrup ") can be for example about 2-40wt%.Usually, this transformation efficiency is preferably about 5-20%.When transformation efficiency is too high, the easy deterioration of the processibility of contact adhesive composition.For example, the trend that has the composition that does not contain the liquid medium form substantially (non--type of solvent) be difficult to the paintable performance that obtains to show at normal temperatures.On the other hand, when transformation efficiency is crossed when low, unstable easily by the characteristic of contact adhesive composition being solidified the pressure sensitive adhesive that (normally photocuring) obtain, in addition, the viscosity of said composition may be crossed low and can not apply.
In addition, with the transformation efficiency of following method determining section polymerisate.That is, from partially polymerized product, take out the about 0.5g sample and the (weight: W of weighing P1).Then sample is heated to 130 ℃ 2 hours so that unconverted monomer volatilization, and will heat remaining samples weighing (weight: W afterwards P2).Further, can be used for following equation by the value that each is obtained and determine transformation efficiency:
Transformation efficiency [%]=(W P2/ W P1) * 100
Contact adhesive composition disclosed herein can be for for example wherein being dissolved in or being scattered in the composition (type of solvent, aqueous solution type, emulsion type etc.) of the form in the suitable liquid medium (it can be organic solvent, water or its mixture) by the acrylic copolymer that most monomer mixture polymerization is obtained.The contact adhesive composition of these forms usually like this constitutes: make and go up and solvent is removed (being about to composition dries) by this contact adhesive composition being applied in suitable substrates etc. from the product that applies, can form and have the pressure sensitive adhesive layer of acrylic copolymer as matrix polymer.At this moment, if desired, can carry out suitable crosslinking Treatment etc.
For comprising by acrylic copolymer (it can be the acrylic copolymer material that does not contain unconverted monomer substantially) that most monomer mixture polymerization is obtained contact adhesive composition as main component, the method that is used for polymeric monomer intermixture is not particularly limited, but can be aptly with mode identical in the partially polymerized situation of monomer mixture is used the known polymerization process of various routines.For example, if acrylic copolymer for example forms by solution polymerization process, then the embodiment of solution polymerization is not particularly limited, and can be by using for example various known monomer supply methods aptly, polymerizing condition (polymerization temperature, polymerization time, polymerization pressure etc.), material (polymerization starter, tensio-active agent etc.) to be used are undertaken by the embodiment identical with the known regular solution polymerization of routine.As the monomer supply method, can use any method for example to be used for the monomer mixture of all measuring is sent into the intermittent feeding method of reaction vessel, continuous supply (dropping) method of supplying with (dropping) method or substep etc. simultaneously.In preferred embodiments, exemplified wherein that preparation is dissolved in the solution that obtains in the solvent by monomer mixture and the initiator that will all measure in reaction vessel, then with the embodiment of monomer mixture batchwise polymerization (batchwise polymerization).Preferred this batchwise polymerization is because this carries out converging operation and process control easily.In another preferred embodiment, exemplified and wherein in reaction vessel, prepared initiator (being generally), then the monomer mixture polymerization has been made simultaneously the drips of solution that is dissolved in the solvent be added to the embodiment that (drips polymerization or successive polymerization) in the reaction vessel by initiator being dissolved in the solution that obtains in the solvent.Usually the monomer mixture of a part (some kinds and/or part ratio) is put into reaction vessel with solvent, remaining mixture can be added drop-wise in the reaction vessel then.
The example of thermal polymerization comprises azo compound (azo-initiator) for example 2,2 '-azobis isobutyronitrile, 2,2 '-azo is two-the 2-methylbutyronitrile, dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo is two-the 4-cyanopentanoic acid, the two isovaleronitriles of azo, 2, two (2-amidine propane) dihydrochlorides of 2 '-azo, 2, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two (the 2-methyl-prop amidine) dithionates of 2 '-azo, 2, two (the N of 2 '-azo, N '-dimethylene NSC 18620) dihydrochloride and 2, two [N-(2-the propyloic)-2-methyl-prop amidine] hydrates of 2 '-azo; Persulphate is Potassium Persulphate and ammonium persulphate for example; Superoxide (peroxide initiator) is dibenzoyl peroxide, tert butyl permaleic acid, tert-butyl hydroperoxide and hydrogen peroxide for example; The ethane class initiator that replaces is the ethane of phenyl replacement for example; The redox system initiator is persulphate and the combination of sodium bisulfite and the combination of superoxide and sodium ascorbate for example.Under situation, can use the polymerization temperature of for example about 20-100 ℃ (40-80 ℃ usually) aptly by thermopolymerization method polymeric monomer intermixture.
In the preferred embodiment of disclosed contact adhesive composition, said composition comprises linking agent in this article.By using linking agent, the pressure sensitive adhesive layer that is formed by composition can have suitable force of cohesion and bounding force, and can improve the anti-repellency of pressure sensitive adhesive layer.Select any linking agent aptly in the known material of various routines from the pressure sensitive adhesive field.For example can use isocyanate ester compound (isocyanates linking agent), epoxies linking agent, aziridines linking agent, melamine class linking agent, metallo-chelate class linking agent, metallic salt linking agent, peroxide linking agent, oxazoline class linking agent, ureas linking agent, amino class linking agent, carbodiimide class linking agent, coupling agent class linking agent (for example silane coupling agent) etc.These linking agents can be used in combination separately or with it.Can preferably this linking agent be blended into wherein will be dissolved in or be scattered in the composition of the form in the suitable liquid medium as the binder composition of type of solvent by the acrylic copolymer that most monomer mixture polymerization forms.Wherein preferably use the isocyanates linking agent.In preferred embodiments, only use one or more (being generally a kind of) isocyanates linking agents as linking agent.As selection, in the scope of not remarkably influenced effect of the present invention, linking agent and the isocyanates linking agent that is different from the isocyanates linking agent can be used in combination.
The example of isocyanate ester compound comprises aliphatic polyisocyanate for example 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl isophthalic acid, 5-pentane vulcabond, 3-methyl isophthalic acid, 5-pentane vulcabond, lysinediisocyanate etc.; Alicyclic polyisocyanates is isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation tetramethylxylene diisocyanate etc. for example; Aromatic polyisocyanate for example 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-phenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 2,2 '-diphenyl propane-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, between-phenylene vulcabond, right-phenylene vulcabond, naphthalene-1, the 4-vulcabond, naphthalene-1, the 5-vulcabond, 3,3 '-dimethoxy phenylbenzene-4,4 '-vulcabond etc.; The araliphatic polyisocyanates is dimethylbenzene-1 for example, 4-vulcabond, dimethylbenzene-1,3-vulcabond etc.
In addition, as the isocyanates linking agent, the dipolymer of the isocyanate ester compound that exemplifies more than can using or trimer, reaction product or polymerisate (for example reaction product of the reaction product of the dipolymer of diphenylmethanediisocyanate or trimer, TriMethylolPropane(TMP) and tolylene diisocyanate, TriMethylolPropane(TMP) and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyethers polyisocyanates, polyester polyisocyanates) etc.For example, can preferably use the reaction product of TriMethylolPropane(TMP) and tolylene diisocyanate.
(polymerisation conversion of the monomer mixture in contact adhesive composition is about under 100% the situation based on 100 weight parts monomers mixtures, it is usually corresponding to 100 parts by weight of acrylic analog copolymers), the amount of the isocyanates linking agent that use can be for example about 0.01-20 weight part (preferably about 0.01-15 weight part).Cross when low when the amount of the linking agent that will use, be difficult to show enough effects (improving the effect of pressure sensitive adhesion performance), and when its consumption is too high, destroy the balance between the adhesion characteristic easily.Usually, based on 100 weight parts monomers mixtures, use the isocyanates linking agent of about 0.01-1 weight part (preferably about 0.02-1 weight part, for example about 0.05-0.5 weight part) aptly.
Disclosed in this article contact adhesive composition is to comprise under monomer mixture or the situation of its partially polymerized product as the composition (normally photo curable binder composition) of main component, can preferably use multifunctional (methyl) acrylate (monomer that promptly contains two or more (methyl) acryl at an one intramolecularly) as linking agent.For example, can use one or more that are selected from multifunctional (methyl) acrylate of in the description of monomer m4, exemplifying.Its suitable example comprises two (methyl) vinylformic acid 1,6-hexylene glycol ester, trimethylolpropane tris (methyl) acrylate, four (methyl) vinylformic acid pentaerythritol ester and two (methyl) vinylformic acid 1 ester.From polymerisation reactivity viewpoints such as (crosslinking reactions), preferably use polyfunctional acrylic ester.For the contact adhesive composition of the partially polymerized product with monomer mixture as main component, preferably that monomer mixture is partially polymerized, then with polyfunctional monomer and its blend (i.e. back-adding).In preferred embodiments, as linking agent, use only one or more (being generally a kind of) multifunctional (methyl) acrylate.As selection, in the scope of not remarkably influenced effect of the present invention, can be used in combination the linking agent (for example isocyanates linking agent) that is different from multifunctional (methyl) acrylate.
Based on 100 weight parts monomers mixtures, the amount that is used for multifunctional (methyl) acrylate of blend as linking agent is for example about 0.001-5 weight part, and is suitably about 0.005-1 weight part (for example about 0.005-0.1 weight part) usually.When the amount of multifunctional (methyl) acrylate that will use is too low, do not show competent cross-linking effect, and the trend that has force of cohesion or anti-repellency to reduce.On the other hand, when the amount of multifunctional (methyl) acrylate that will use was too high, it is too high that the elasticity of the pressure sensitive adhesive that forms after curing increases, and bounding force or tackiness (tackiness) may reduce easily.
In the pressure sensitive adhesive layer on being arranged on pressure sensitive adhesion sheet disclosed herein, this pressure sensitive adhesive layer preferably includes has for example pressure sensitive adhesive of the gel fraction of about 25-75%.In order to form pressure sensitive adhesive with this gel fraction (in comprising the composition of linking agent, being the pressure sensitive adhesive after crosslinked), can be provided with aptly some conditions for example monomer form the kind of the molecular weight of the polymerization degree, the acrylic copolymer of monomer mixture in (amount of the monomer m2 that for example will use), the contact adhesive composition, the condition (drying conditions, rayed condition etc.) that forms pressure sensitive adhesive layer, the linking agent that will use and amount etc.When the gel fraction of pressure sensitive adhesive is too low, there is the trend of insufficient force of cohesion or anti-repellency.On the other hand, when its gel fraction is too high, may reduce pressure sensitive adhesion power or tackiness easily.The pressure sensitive adhesive of the gel fraction by having about 25-75% (for example about 30-60%) scope can be realized better bond properties.
" gel fraction of pressure sensitive adhesive " used herein is meant the value of measuring with following method.Gel fraction can be understood that the weight ratio of the ethyl acetate indissolvable component in the pressure sensitive adhesive.
Be used to measure the method for gel fraction:
With pressure sensitive adhesive sample (weight: W B1) with having the voided polytetrafluoroethylene film (weight: W of 0.2 μ m mean pore size B2) seal pouch, and with its peristome kite string (weight: W B3) fasten.This bag is immersed in the 50mL ethyl acetate, and keep leaving standstill 7 days down in room temperature (common 23 ℃).Then bag is taken out, and wipe the ethyl acetate of staying on bag outside surface.Bag was descended dry 2 hours at 130 ℃, and measure the weight (W of bag B4).By each numerical value being used for the gel fraction that following equation is determined pressure sensitive adhesive:
Gel fraction [%]=[(W B4-W B2-W B3)/W B1] * 100
In addition, wish to use the commodity " NITOFLON (registered trademark) NTF1122 " by name that can obtain from Nitto Denko Corporation (mean pore size: 0.2 μ m, porosity: 75% and thickness: 85 μ m) or its equivalent material as porous Teflon (PTFE) film.
Contact adhesive composition disclosed herein can be included in various additives commonly used in the contact adhesive composition field as optional component.The example of component that should be optional comprises tackifier (rosin based resin, petroleum resinoid, terpenoid resin, phenolic resinoid, ketone resin etc.), softening agent, tenderizer, filler, tinting material (pigment, dyestuff etc.), oxidation inhibitor, labelled reagent, stablizer and sanitas.These additives can use, and not characterize the present invention especially by common method, the conventional known substances of use.Therefore, in the detailed description of this omission about it.
In addition, in order to regulate the purpose of viscosity (being generally thickening), can be aptly with contact adhesive composition disclosed herein and the polymer blending except the multipolymer that forms by the monomer mixture polymerization.The use of polymkeric substance that is used to regulate viscosity is effective especially for having monomer mixture or its partially polymerized product contact adhesive composition (normally photo curable binder composition) as main component.The example that is used to regulate the polymkeric substance of viscosity comprises styrene-butadiene rubber(SBR) (SBR), synthetic polyisoprene (IR), styrene butadiene-styrene block copolymer (SBS), ethane-acetic acid ethyenyl base co-polymer, acrylic rubber, urethane, polyester etc.In addition, can use by making acrylic polymers that alkyl (methyl) acrylate and function monomer (for example be selected from acrylic monomer with functional group such as acrylamide, vinyl cyanide, acryloyl morpholine, vinylformic acid etc. one or more) copolymerization obtains as being used to regulate the polymkeric substance of viscosity.The preferred polymkeric substance that is used to regulate viscosity that does not contain carboxyl (acidic-group except carboxyl more preferably) substantially that uses.
These polymkeric substance that are used to regulate viscosity can use separately or be used in combination with it, but based on the whole pressure sensitive adhesive that forms with contact adhesive composition, and they are preferably with the amount use of (about usually 5-40wt%) below about 40wt% scope.That is, the ratio that preferably is used for regulating the polymkeric substance of viscosity is about 40wt% following (more preferably from about below the 20wt%) of the component of the formation pressure sensitive adhesive that is contained in composition approximately.
Contact adhesive composition disclosed herein is preferred to be constituted like this: make the acrylic copolymer that the monomer mixture polymerization obtains of passing through of about 50wt% above (more preferably from about more than the 70wt%, for example more than the 90wt%) be contained in the pressure sensitive adhesive with said composition formation.This binder composition can form the pressure sensitive adhesive with better bond properties.
Pressure sensitive adhesion sheet according to the present invention comprises the pressure sensitive adhesive layer that forms with any contact adhesive composition disclosed herein.It can be the pressure sensitive adhesion sheet that is bonded on the base material, wherein this pressure sensitive adhesive layer is set to be fixed in the pressure sensitive adhesion sheet on surface or two surfaces (be not intended to pressure sensitive adhesive layer is separated from base material) of flat substrates (supporting mass), the pressure sensitive adhesion sheet that does not perhaps have base material, wherein pressure sensitive adhesive layer is arranged on the supporting mass for example on the barrier liner (resin sheet of isolation processing etc. is carried out on interleaving paper, its surface) with isolating power.Notion about the pressure sensitive adhesion sheet mentioned herein comprises those that are called as pressure-sensitive adhesive tape, pressure sensitive adhesion label, pressure sensitive adhesion film etc.In addition, those that pressure sensitive adhesive layer is not limited to form continuously, but it can be for example with the regular pattern binder layer that forms of point-like, strip etc. or irregular pattern for example.
Pressure sensitive adhesion sheet disclosed herein can be for for example having the pressure sensitive adhesion sheet of the cross-sectional structure that schematically shows in Fig. 1-6.Wherein, Fig. 1 and Fig. 2 are the examples that is bonded in the pressure sensitive adhesion chip architecture of the double-sided pressure-sensitive adhesive type on the base material.Pressure sensitive adhesion sheet 11 as shown in fig. 1 is included in the pressure sensitive adhesive layer 2 on base material 1 two sides, and pressure sensitive adhesive layer 2 is constructed separately like this: make at least one barrier liner 3 of wearing isolation surface that their are had at pressure sensitive adhesive layer protect.Pressure sensitive adhesion sheet 12 is as shown in Figure 2 constructed like this: make the two sides of base material 1 be provided with pressure sensitive adhesive layer 2, and at least one of these binder layers had barrier liner 3 protections that have isolation surface on the two sides of pressure sensitive adhesive layer.This pressure sensitive adhesion sheet 12 can be constructed like this: if make that then the pressure sensitive adhesive layer on the another side contacts with the back side of barrier liner 3, and the pressure sensitive adhesive layer on the another side is also protected by barrier liner 3 with pressure sensitive adhesion sheet 12 coilings.
Fig. 3 and Fig. 4 are the examples that does not have the pressure sensitive adhesion chip architecture of base material.Pressure sensitive adhesion sheet 13 is as shown in Figure 3 constructed like this: make do not have that the two sides of the pressure sensitive adhesive layer 2 of base material had a pressure sensitive adhesive layer at least one wear isolation surface barrier liner 3 protections.Pressure sensitive adhesion sheet 14 as shown in Figure 4 can be constructed like this: making does not have the one side of the pressure sensitive adhesive layer 2 of base material to be had barrier liner 3 protections of isolation surface by the two sides; if and this sheet material reeled, then the another side of pressure sensitive adhesive layer 2 contacts with barrier liner 3 and this another side is also protected by barrier liner 3.
Fig. 5 and Fig. 6 are the examples that is bonded in the pressure sensitive adhesion chip architecture of the single face pressure sensitive adhesion type on the base material.Pressure sensitive adhesion sheet 15 is as shown in Figure 5 constructed like this: make the one side of base material 1 be provided with pressure sensitive adhesive layer 2, and the surface of pressure sensitive adhesive layer 2 (adhesive face) had at least one barrier liner 3 protections of wearing isolation surface of pressure sensitive adhesive layer.Pressure sensitive adhesion sheet 16 is as shown in Figure 6 constructed like this: make the one side of base material 1 have pressure sensitive adhesive layer 2.It can be constructed like this: make the another side of base material 1 have isolation surface, and if with pressure sensitive adhesion sheet 16 coilings, then pressure sensitive adhesive layer 2 contacts with another side, and the surface of pressure sensitive adhesive layer (adhesive face) is protected on the another side of base material 1.
Forming the base material of pressure sensitive adhesion sheet can for example select from following and use aptly according to the application of pressure sensitive adhesion sheet: plastics film is polypropylene film, ethylene-propylene copolymer film, polyester film and polyvinyl chloride film for example; The foams base material is urethane foam and polyethylene foam for example; Paper is kraft paper, goffered paper and Japan paper for example; Cloth is cotton and staple fibre for example; Non-woven fabric is polyester nonwoven thing and vinylon non-woven fabric for example; Tinsel is aluminium foil and Copper Foil etc. for example.As plastics film, can use the film of non--tensile film and stretching (uniaxial extension or biaxial stretch-formed).In addition, can with the one side that is provided with pressure sensitive adhesive layer in the base material with priming paint apply, surface treatment such as Corona discharge Treatment.The thickness of base material can be selected according to purpose aptly, but generally speaking, it is about 10 μ m-500 μ m (common 10 μ m-200 μ m) usually.
Pressure sensitive adhesive layer can preference as by with any contact adhesive composition disclosed herein, promptly has monomer mixture or its partially polymerized product contact adhesive composition as main component, place on (being applied in usually) supporting mass (base material or barrier liner), and by being cured (polymerization) and forming with active energy beam (for example ultraviolet ray) irradiation composition.For example,, can realize more suitably result by this method that forms pressure sensitive adhesive layer from the thermotolerance viewpoint of pressure sensitive adhesive layer.In this formation method, the synthetic acrylic copolymer (matrix polymer in the pressure sensitive adhesive layer) that obtains by the monomer mixture polymerization, and form pressure sensitive adhesive layer simultaneously.The binder composition that the active energy beam that this method can be preferably applied to prepare in the following manner is curable: with monomer mixture (mixture of unconverted monomer) or by with monomer mixture with suitable polymerization process (for example light polymerization process) with the partially polymerized partially polymerized product that obtains of Photoepolymerizationinitiater initiater with linking agent (multifunctional (methyl) acrylate etc.) blend of using as required.The curable binder composition of this active energy beam can be the composition (non-solvent) that does not contain liquid medium (organic solvent, water etc.) substantially.The curable binder composition of active energy beam for the form that comprises liquid medium preferably will be arranged on the composition dries on the supporting mass, then with the active energy beam irradiation thereon.
In addition, pressure sensitive adhesive layer also can be gone up and composition dries is formed by any contact adhesive composition disclosed herein being placed (being applied in usually) supporting mass (base material or barrier liner).This method that is used to form pressure sensitive adhesive layer can be preferred for the contact adhesive composition of such form: wherein will be dissolved in advance or be scattered in the liquid medium by acrylic copolymer and the linking agent that uses as required, the additive etc. that most monomer mixture polymerization is obtained.Comprise at contact adhesive composition under the situation of linking agent, if desired, except above-mentioned drying, can also carry out suitable crosslinked.
The applying of contact adhesive composition can be used coater commonly used, and for example intaglio plate roller coating machine, reverse coater, kiss-roll coater, dipping roller coating machine, rod are coated with machine, cutter is coated with machine, spraying machine etc. and carries out.From promoting crosslinking reaction, improve the viewpoint of preparation efficiency etc., can be preferably under heating with the contact adhesive composition drying.Be used for the exsiccant temperature and depend on the supporting mass type that applies composition thereon and change, but can use for example about 40-150 ℃ drying temperature.
In addition, under the situation that is bonded in the pressure sensitive adhesion sheet on the base material, contact adhesive composition directly can be placed and form pressure sensitive adhesive layer on the base material, and the pressure sensitive adhesive layer that is formed on the barrier liner can be transferred on the base material.
The thickness of pressure sensitive adhesive layer is not particularly limited, but is generally for example about 10 μ m above (more than preferred about 20 μ m, more preferably from about more than the 30 μ m), the bond properties that can realize (for example bond strength) thus.In addition, usually preferred this thickness is about 400 μ m following (below about 200 μ m, for example about 100 μ m are following usually).
Embodiment
Hereinafter described several embodiments of the present invention, but do not thought and the invention is intended to be limited to these embodiment.In addition in the following description, " part " and " % " is based on weight, unless explanation especially in addition.
Embodiment 1
To comprising 70 parts of 2-EHA (2EHA, the Tg:-70 of homopolymer ℃), 30 parts of N-vinyl-2-Pyrrolidone (NVP, the Tg:54 of homopolymer ℃) and 4 parts of N-hydroxyethyl acrylamide (HEAA, the Tg:98 of homopolymer ℃) 100 parts of monomer mixtures in, 0.05 part 2 of blend, 2-dimethoxy-1,2-diphenylethane-1-ketone (trade(brand)name " Irgacure 651 " (being produced by Ciba Japan)) and 0.05 part of 1-hydroxycyclohexylphenylketone (trade(brand)name " Irgacure 184 " (being produced by Ciba Japan)) are as Photoepolymerizationinitiater initiater.By under nitrogen atmosphere, stirring dissolved oxygen is fully removed from this mixture, and with uviolizing to mixture, thereby obtain by the partially polymerized (transformation efficiency (monomer conversion): the acrylic copolymer that obtains about 11%) of monomer mixture.For this monomer syrup, add 0.01 part of diacrylate 1 based on 100 parts of monomer mixtures, 6-hexylene glycol ester (HDDA) is as internal crosslinking agent.Make photo curable contact adhesive composition thus according to embodiment 1.
Two barrier liner (thickness: 38 μ m) of having used silicone separant isolation processing of preparation on the surface of polyethylene terephthalate (PET) film.Above-mentioned contact adhesive composition is applied on the isolation surface (surface of handling) of first barrier liner with separant.Regulate applied amounts simultaneously so that the binder layer that finally obtains has 50 μ m thickness.Then, the isolation surface of the binder composition that applies and second barrier liner is pasted.Further pass through at about 4mW/cm 2Light intensity and about 720mJ/cm 2The light quantity condition under irradiation ultraviolet radiation, make composition solidify to form pressure sensitive adhesive layer.Thus, make pressure sensitive adhesion sheet (barrier liner agglutinating adhesive sheet), it is constructed like this: make the two sides of pressure sensitive adhesive layer be protected by barrier liner.
Measure the gel fraction of composition in the following manner according to the method that is used to measure gel fraction according to the pressure sensitive adhesive of the pressure sensitive adhesion sheet pressure sensitive adhesive layer of present embodiment.Promptly, preparation has the porous ptfe film (trade(brand)name " NITOFLON (registered trademark) NTF1122 " of 100mm * 100mm size, produce by Nitto Denko Corporation) and have about 100mm length (fineness: kite string 1.5mm), and measure its weight.Is 20cm with two barrier liners from cut lengths 2Barrier liner agglutinating pressure sensitive adhesion sheet on peel off, and the pressure sensitive adhesive sample is sealed pouch, and its peristome is fastened with kite string with the PTFE film.Measure the weight of bag, and deduct the weight (W of PTFE film by the weight of bag B2) and the weight (W of kite string B3) to determine the weight (W of pressure sensitive adhesive sample B1).Then this bag is immersed in the 50mL ethyl acetate, and keep leaving standstill 7 days down in room temperature (common 23 ℃).Then bag is taken out from ethyl acetate, and wipe the ethyl acetate of staying on bag outside surface.Bag was descended dry 2 hours at 130 ℃ in drying machine, measure the weight (W of bag then B4).The gel fraction of definite pressure sensitive adhesive is 49.9% by each numerical value is used for foregoing equation.
Embodiment 2-5
(in this table, " AA " represents vinylformic acid except using the monomer mixture of forming shown in the table 1; The Tg:106 of homopolymer ℃) and the amount of the HDDA that adds is respectively 0.02 part in embodiment 3 and is outside 0.04 part in embodiment 5, with with embodiment 1 in identical mode prepare contact adhesive composition, and prepare pressure sensitive adhesion sheet based on 100 parts of monomer mixtures.With with embodiment 1 in the gel fraction of the pressure sensitive adhesive measured of identical mode be 48% in embodiment 2 respectively, be 68.1% in embodiment 3, be 81.9% in embodiment 4 and be 60% in embodiment 5.
For the pressure sensitive adhesion sheet for preparing among the embodiment 1-5 (it is provided with the pressure sensitive adhesive layer that is formed by the UV curable adhesives composition), carry out following evaluation test.
Corrodibility:
With a barrier liner from peeling off according to the pressure sensitive adhesion sheet of each embodiment so that the one side of pressure sensitive adhesive layer exposes, and will have clear PET film (it is not through the isolation processing) bonding of 25 μ m thickness and supporting mass thereon.In addition, the barrier liner on the another side peeled off, and itself and the Copper Foil with 80 μ m thickness are pasted and combination, remain on following 250 hours of the atmosphere of 60 ℃ * 95%RH then so that the another side of pressure sensitive adhesive layer exposes.With the naked eye at the copper foil surface of unilateral observation of PET film and pressure sensitive adhesion sheet adhesive portion, use the colour-change of copper foil surface to confirm to exist or do not exist copper foil surface corrodibility subsequently as index.As a result, the situation that the affirmation copper foil surface does not have colour-change is represented as " not existing " corrodibility, and confirms that the situation of copper foil surface colour-change is represented as " existence " corrodibility.
Bounding force:
With a barrier liner from peeling off according to the pressure sensitive adhesion sheet of each embodiment so that the one side of pressure sensitive adhesive layer exposes, and will have PET film (it is not through the isolation processing) bonding of 50 μ m thickness and supporting thereon.It is wide with the preparation test piece that the pressure sensitive adhesion sheet of this supporting is cut into 25mm.As treating the agglutinating object, use the clean acrylic acid or the like plate that obtains for 10 times by with cleaning waste (clean waste) reciprocating friction that wherein immerses Virahol and cleaning.Barrier liner on the another side is peeled off from test piece, and in the mode of a roll-in of 5kg roller it is pressed in and treats on the agglutinating object.It, with its taking-up, is being kept leaving standstill 30 minutes under the measurement environment of 23 ℃ * 50%RH, and using tension tester to measure stripping strength (N/25mm) under the condition of 300mm/min draw speed and 180 ° of peel angle after 2 days in storage under 40 ℃.
Anti-repellency:
To be cut into the size that 10mm is wide and 90mm is long according to the pressure sensitive adhesion sheet of each embodiment, and barrier liner will be peeled off from one side.Then, (thickness: aluminium sheet 0.5mm) and its bonding and combination are with the preparation test piece will to have same size.With this test piece in the vertical along The line bending of 50mm (being the curvature of R50), aluminium sheet in order to avoid towards interior.Then, barrier liner is peeled off from the test piece another side, and used laminating machine that it is compressed on the polypropylene board surface of cleaning in the same manner as described above so that float (floating) do not occur.It is stayed left standstill in 23 ℃ of environment 4 hours or 7 hours, measure on the polypropylene board surface flying height at test piece edge (mm) in the vertical then.Two ends in test piece are measured, and regard the total float height value at two ends as anti-repellency value.
Confining force:
As the index of force of cohesion, estimate confining force (static load feature) in the following manner according to the pressure sensitive adhesion sheet of each embodiment.That is, the barrier liner on the one side is peeled off so that the one side of pressure sensitive adhesive layer exposes from pressure sensitive adhesion sheet, and will be had PET film (it is not through the isolation processing) bonding of 50 μ m thickness and supporting thereon.The adhesive sheet of this supporting is cut into the wide size of growing with 50mm of 10mm with the preparation test piece.As treating the agglutinating object, use the clean hard rubber sheet that cleans for 10 times by with cleaning waste (clean waste) reciprocating friction that wherein immerses toluene.Barrier liner on the another side is peeled off from test piece, and with the 2kg roller on the long contact area of the wide and 20mm of 10mm back and forth the mode of roll-in it be pressed in treat on the agglutinating object.Holding it in 40 ℃ after following 30 minutes, under 40 ℃ of environment, hard rubber sheet is taken off, and the 500g load is given to test piece free end (protuberance of hard rubber sheet) afterwards, it was left standstill 2 hours under 40 ℃ of environment.After giving load and before 2 hours subsequently, test piece is represented as " bad " confining force from the situation that the agglutinating object falls, even and the situation that back test piece in the past remained on the agglutinating object at 2 hours is represented as " good " confining force.
The results are shown in the table 1 of evaluation test.In this table, be used to prepare composition (the monomeric kind that will use and the ratio of amount) according to the monomer mixture of the contact adhesive composition of each embodiment with illustrating by forming definite Tg based on the Fox equation.
Table 1
Figure A20091020295600371
As shown in table 1, comprise monomer m1 (2EHA) and monomer m3 (NVP) with having among the present invention and do not comprise that the pressure sensitive adhesion sheet (embodiment 3) that the copolymerization of monomer m2 is formed compares, according to pressure sensitive adhesion sheet (embodiment 1 and 2) with the copolymerization composition that except monomer m1 and m3, also comprises monomer m2 (being HEAA) here, significantly improved anti-repellency, other characteristics keep quite simultaneously.Therefore, compare,, can realize being equal to or higher levels of anti-repellency and stripping strength by the pressure sensitive adhesion sheet of embodiment 1 and 2 with the pressure sensitive adhesion sheet of the embodiment 5 that obtains by the carboxylic monomer (being AA here) that uses general binder composition.In addition, the pressure sensitive adhesion sheet according to the monomer m3 with a large amount of embodiment 4 is not enough on the balance between the adhesion characteristic.In addition, on the metallic surface, do not have corrodibility according to the pressure sensitive adhesion sheet of embodiment 1-4, and have enough confining forces yet.On the other hand, affirmation shows beguine according to the better adhesion characteristic of the pressure sensitive adhesion sheet of embodiment 3 by the pressure sensitive adhesion sheet of the embodiment 5 that use AA obtains, but its erode metallic surfaces.
Embodiment 6 and 7
(in this table, " BA " represents butyl acrylate except using the monomer mixture of forming shown in the table 2; The Tg:-54 of homopolymer ℃) and for embodiment 6 or 7, the amount of the HDDA that will add based on 100 parts of monomer mixtures is outside 0.03 part, with with embodiment 1 in identical mode prepare contact adhesive composition, and use said composition to prepare pressure sensitive adhesion sheet.The gel fraction of pressure sensitive adhesive is respectively 28.7% in embodiment 6 and is 53% in embodiment 7.
Embodiment 8 and 9
(in this table, " DEAA " represents N, N-diethyl acrylamide except using the monomer mixture of forming shown in the table 2; The Tg:81 of homopolymer ℃) and based on 100 parts of monomer mixtures, the amount of the HDDA that adds is respectively 0.05 part in embodiment 8 and is outside 0.06 part in embodiment 9, with with embodiment 1 in identical mode prepare contact adhesive composition, and use said composition to prepare pressure sensitive adhesion sheet.The gel fraction of pressure sensitive adhesive is respectively 30.2% in embodiment 8 and is 19.7% in embodiment 9.
Carry out above-mentioned evaluation test for the pressure sensitive adhesion sheet that in embodiment 6-9, prepares (it is provided with the binder layer that the binder composition by the UV curable type forms).The results are shown in the table 2.
Table 2
Figure A20091020295600391
From relatively finding out between embodiment 6 and 7, with comprising monomer m1 (BA) and monomer m3 (NVP) and not comprising that the pressure sensitive adhesion sheet (embodiment 7) that the copolymerization of monomer m2 is formed compares among the present invention, by the pressure sensitive adhesion sheet (embodiment 6) that the copolymerization that replaces a part of NVP here with monomer m2 (being HEAA) is formed, obviously improve other characteristics maintenances simultaneously of anti-repellency quite.From relatively finding out between embodiment 8 and 9, with comprising monomer m1 (2EHA) and monomer m3 (DEAA) and not comprising that the pressure sensitive adhesion sheet (embodiment 9) that the copolymerization of monomer m2 is formed compares among the present invention, the pressure sensitive adhesion sheet of forming by the copolymerization that replaces a part of DEAA with HEAA (embodiment 8), obviously improve anti-repellency and confining force, stripping strength keeps quite simultaneously.In addition, all pressure sensitive adhesion sheets of embodiment 6-9 do not have corrodibility on the metallic surface.
Embodiment 10
In the reaction vessel that is equipped with cooling tube, nitrogen inlet tube, thermometer and agitator, put into 0.2 part 2,2 '-azobis isobutyronitrile (AIBN) as polymerization starter, 70 parts of 2EHA, 26 parts of NVP and 4 parts of HEAA as monomer mixture, with ethyl acetate as solvent, at room temperature under nitrogen atmosphere, stirred 1 hour subsequently.After this content in the reaction vessel (solution that contains the monomer mixture of whole amounts) is heated to 60 ℃, makes its polymerization 5.5 hours in nitrogen gas stream.By the solution polymerization of this intermittent feeding type, obtain acrylic polymers solution.
In the acrylic polymers solution that obtains, add (with solid content meter based on 100 parts of acrylic polymerss, this will be used for hereinafter), its amount is 0.2 part reaction product (the commodity in use name " CORONATE L " as the TriMethylolPropane(TMP) and the tolylene diisocyanate of isocyanates linking agent, by NIPPON POLYURETHANEINDUSTRY CO., LTD. produces).Prepare contact adhesive composition thus according to embodiment 10.
Two barrier liner (thickness: 38 μ m) of having used silicone separant isolation processing of preparation on the surface of polyethylene terephthalate (PET) film.With coater above-mentioned binder composition is applied on the isolation surface (surface of handling with separant) of first barrier liner, drying is 3 minutes under 130 ℃, forms the pressure sensitive adhesive layer with 50 μ m thickness on barrier liner.Then, the isolation surface with this pressure sensitive adhesive layer and second barrier liner makes up.Thus, pressure sensitive adhesion sheet (barrier liner agglutinating pressure sensitive adhesion sheet) is constructed like this: make to make the double-sided pressure-sensitive adhesive agent layer of being protected by barrier liner.With with embodiment 1 in the gel fraction of the pressure sensitive adhesive measured of identical mode be 49.2%.
Embodiment 11
Except using the monomer mixture of forming shown in the table 3 (in this table, " HEA " represents Hydroxyethyl acrylate) and based on 100 parts of acrylic polymerss, the amount of the isocyanates linking agent that adds is outside 0.1 part, with with embodiment 10 in identical mode prepare contact adhesive composition, and use said composition to prepare pressure sensitive adhesion sheet.The gel fraction of this pressure sensitive adhesive is 59.4%.
Embodiment 12
Except using the monomer mixture of forming shown in the table 3 (in this table, " CHMI " represents N-cyclohexyl maleimide) and based on 100 parts of acrylic polymerss, the amount of the isocyanates linking agent that adds is outside 0.5 part, with with embodiment 10 in identical mode prepare contact adhesive composition, and use said composition to prepare pressure sensitive adhesion sheet.The gel fraction of this pressure sensitive adhesive is 53.4%.
For carrying out aforesaid evaluation test on the pressure sensitive adhesion sheet that in embodiment 9-12, prepares (it is provided with the binder layer that is formed by the Solvent Adhesive composition).The results are shown in the table 3.
Table 3
Figure A20091020295600411
As shown in table 3, according to having the pressure sensitive adhesion sheet that in monomer mixture, replaces the copolymerization composition of HEA (embodiment 11), further improve other characteristics of anti-repellency (reduction of flying height total value) while and keep suitable at least with the HEAA (embodiment 10) of equivalent.In addition, by the pressure sensitive adhesion sheet that the copolymerization with HEAA (embodiment 10) the replaced C HMI (embodiment 12) that uses equivalent in monomer mixture is formed, find out the effect that improves bond properties similarly.In addition, on the metallic surface, do not have corrodibility according to all pressure sensitive adhesion sheets of embodiment 10-12, and show enough confining forces.
As implied above, describe specific embodiments of the invention in detail, these only are used to the purpose explained, and do not limit the scope of claim.Technology described in the claim scope comprises the various improvement and the variation of aforesaid specific embodiment.
Although at length and with reference to its specific embodiments described the present invention, it is evident that: can in not departing from its spirit and scope, make various changes and improvements for those skilled in the art.
The application is based on Japanese patent application (the patent application No.2008-198269 that the patent application No.2008-135518 that on May 23rd, 2008 submitted to and on July 31st, 2008 submit to), and the whole contents of these patent applications is hereby incorporated by.
As mentioned above, the pressure sensitive adhesion sheet that is provided with the pressure sensitive adhesive layer that the contact adhesive composition of the application of the invention forms shows excellent adhesion performance (anti-repellency, static load characteristic etc.) at normal temperatures, in addition except electronic unit, its can preference as be used to have product with metallic surface fixing, as the matrix material of erode metallic surfaces performance with inhibition.This pressure sensitive adhesion sheet can be preferred for using at other that are used for being applied directly to embodiment on the metallic surface, for example is used for for example having the application of the transportation, protection, decoration etc. of product with metallic surface, produces the advantage of these characteristics.Contact adhesive composition of the present invention is suitable as the contact adhesive composition of the pressure sensitive adhesion sheet (being generally used for forming the pressure sensitive adhesive layer of pressure sensitive adhesion sheet) that is used for being bonded on the metallic surface.In addition, can be used for other application implementation schemes aptly, be not limited to directly be bonded in the embodiment on the metallic surface, because its bond properties that shows at normal temperatures as mentioned above by pressure sensitive adhesion sheet provided by the invention.

Claims (8)

1. contact adhesive composition, its comprise monomer mixture or by with the partially polymerized at least acrylic copolymer material that obtains of this monomer mixture as main component,
Described monomer mixture comprises:
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m 1) that is selected from by alkyl (methyl) acrylate of following formula (I) expression of 50-85wt%:
CH 2＝C(R 1)COOR 2 (I)
R wherein 1Be hydrogen atom or methyl, and R 2For having the alkyl of 1-20 carbon atom,
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m2) that is selected from by N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression of 0.1-12wt%:
CH 2＝C(R 3)CONHR 4 (II)
R wherein 3Be hydrogen atom or methyl, and R 4For hydroxyalkyl with 2-4 carbon atom and
Based on the total amount of monomer mixture, its amount is at least a N-of the being selected from vinyl cyclic amide and the monomer (monomer m3) that can have (methyl) acrylamide of N-alkyl of 10-40wt%; And
Described monomer mixture does not comprise carboxylic monomer substantially.
2. composition according to claim 1 wherein based on the total amount of monomer mixture, comprises monomer m 1, monomer m2 and monomer m3 with the total amount more than the 90wt%.
3. composition according to claim 1, wherein said monomer mixture have the feasible monomer composition that has the second-order transition temperature (Tg) below-10 ℃ by the acrylic copolymer that described monomer mixture polymerization is obtained.
4. composition according to claim 1, wherein said monomer m2 are N-(2-hydroxyethyl) (methyl) acrylamide.
5. composition according to claim 1, wherein said monomer m3 are at least a monomer that is selected from by the N-vinyl cyclic amide of following formula (III) expression:
R wherein 5It is divalent organic group.
6. composition according to claim 1, it is used for directly being bonded in the pressure sensitive adhesion sheet on the metallic surface.
7. pressure sensitive adhesion sheet, it comprises the pressure sensitive adhesive layer by using composition according to claim 1 to form.
8. method of producing pressure sensitive adhesion sheet, described method comprises:
Preparation comprises monomer mixture or by being the contact adhesive composition of 0.01-2 weight part Photoepolymerizationinitiater initiater with the partially polymerized acrylic copolymer material that obtains of monomer mixture with based on 100 weight parts monomers mixtures,
Described monomer mixture comprises:
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m1) that is selected from by alkyl (methyl) acrylate of following formula (I) expression of 50-85wt%:
CH 2＝C(R 1)COOR 2 (I)
R wherein 1Be hydrogen atom or methyl, and R 2For having the alkyl of 1-20 carbon atom,
Based on the total amount of monomer mixture, its amount is at least a monomer (monomer m2) that is selected from by N-hydroxyalkyl (methyl) acrylamide of following formula (II) expression of 0.1-12wt%:
CH 2＝C(R 3)CONHR 4 (II)
R wherein 3Be hydrogen atom or methyl, and R 4For hydroxyalkyl with 2-4 carbon atom and
Based on the total amount of monomer mixture, its amount is at least a N-of the being selected from vinyl cyclic amide and the monomer (monomer m3) that can have (methyl) acrylamide of N-alkyl of 10-40wt%, and
Described monomer mixture does not comprise carboxylic monomer substantially;
Described contact adhesive composition is applied on the supporting mass; With
By this composition that applies is solidified, form pressure sensitive adhesive layer thus.
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CN102453447A (en) * 2010-10-26 2012-05-16 罗门哈斯公司 Removable gluing paster
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Application publication date: 20091125