CN106795406A - Contact panel adhesive composite, adhesive sheet and laminated body - Google Patents
Contact panel adhesive composite, adhesive sheet and laminated body Download PDFInfo
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- CN106795406A CN106795406A CN201580053776.2A CN201580053776A CN106795406A CN 106795406 A CN106795406 A CN 106795406A CN 201580053776 A CN201580053776 A CN 201580053776A CN 106795406 A CN106795406 A CN 106795406A
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- 0 CCC(C***(NNN=C=O)=O)(CO*)CO*C(N*N=*=O)=O Chemical compound CCC(C***(NNN=C=O)=O)(CO*)CO*C(N*N=*=O)=O 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
A kind of contact panel adhesive composite, it contains：(A) weight average molecular weight is 100,000 less than 800,000 and contains substantially no the acrylic acid series polymeric compounds of acidic-group；Crosslinking agent shown in (B) following formulas (1) or following formulas (2), relative to the above-mentioned mass parts of (A) acrylic acid series polymeric compounds 100, contain above-mentioned (B) crosslinking agent more than 0.04 mass parts and below 10 mass parts.
Description
Technical field
The present invention relates to contact panel adhesive composite, adhesive sheet and laminated body.
Background technology
It is mostly to be used in the harsher environment compared with image display such as in-car and outdoor due to contact panel
Under (for example, under high temperature and/or high humidity environment), therefore, constitute the contact panel unit contained by contact panel for laminating
The bonding agent of various components, even if also requiring that the characteristic that can be also played stably under conditions of harsh.
In addition, the outmost surface of picture is configured in as the contact panel unit of the laminated body of various components, therefore quilt
It is required that the transparency higher, simultaneously because moisture is invaded from outside, it is easy in the bond layer contained by the contact panel unit
Produce foaming.Further, since by the gas of the vapor produced by the various components for constituting contact panel unit, carbon dioxide etc.
Body, produces foaming in bond layer sometimes.
And, in recent years, in the contact panel of the electrostatic capacitance mode of main flow, formed sometimes the conducting film of distribution with it is Nian Jie
Agent directly contact.Therefore, will not change conductive membrane property bonding agent requirement.
Conducting film is generally formed as metal or metal oxide as tin indium oxide (ITO), antimony tin (ATO),
Therefore sometimes due to conducting film is contacted with acid and produces corrosion, the resistance value of its result meeting conducting film rises.
On the other hand, in order to improve the heat resistance or humidity resistance of bond layer, generally using the bonding using sour composition
The method of agent.But, as noted previously, as corrosion is easily produced in conducting film, therefore the bonding agent used in contact panel
It is difficult with sour composition.Thus, known adhesive composite will meet bonding force high, high transparency and not corrode conducting film
Characteristic (conducting film non-aggressive) requirement while, it is very tired that can suppress the foaming under the conditions of strict wet-heat resisting
Difficult.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-77287 publications
The content of the invention
Invent problem to be solved
The present invention provide one kind can suppress under wet heat condition foaming and bonding force, durability and the transparency it is excellent,
With the noncorrosive contact panel adhesive composite of conducting film, adhesive sheet and laminated body.
Method for solving problem
In order to solve above-mentioned problem, even it was found by the inventors of the present invention that containing containing substantially no acidic-group
The adhesive composite of acrylic acid series polymeric compounds, by using specific crosslinking agent, can obtain pressing down under wet heat condition
System foaming, and the transparency, bonding force, durability and the excellent adhesive composite of conducting film non-aggressive.
1. the contact panel adhesive composite of a mode of the invention, contains：(A) weight average molecular weight be 100,000 with
It is upper and less than 800,000 and contain substantially no the acrylic acid series polymeric compounds of acidic-group；(B) following formulas (1) or following
Crosslinking agent shown in formula (2)；Above-mentioned (A) acrylic acid series polymeric compounds are contained containing (a1) (methyl) alkyl acrylate and (a2)
The copolymer of the monomer component of the monomer of hydroxyl, relative to the above-mentioned mass parts of (A) acrylic acid series polymeric compounds 100, contains 0.04 matter
Above-mentioned (B) crosslinking agent more than amount part and below 10 mass parts.
(in formula, R1A、R1B、R1CIt independently is containing shown in the group shown in following formulas (3) and/or following formulas (4)
Base group, R2A、R2B、R2CIt is-(CH2)6- shown group.)
(in formula, R1A、R1B、R1CIt independently is containing shown in the group shown in following formulas (3) and/or following formulas (4)
Group group, R2A、R2B、R2C、R3A、R3B、R3C、R3D、R3E、R3FIt is-(CH2)6- shown group.)
(in formula, x is more than 2 and less than 10 integer, and m is more than 1 and less than 10 integer.)
(in formula, X represents singly-bound or-O-, and y is more than 2 and less than 10 integer, and n is more than 1 and less than 10 integer.)
2. the contact panel adhesive composite as described in above-mentioned 1, wherein, above-mentioned monomer component can contain：45 matter
Above-mentioned (a1) (methyl) alkyl acrylate of amount more than % and below 99 mass %；More than 1 mass % and below 40 mass %
Above-mentioned (a2) hydroxyl monomer；Beyond more than 0 mass % and below 15 mass %, (a1) composition and (a2) composition
And there is the monomer of 1 olefinic double bond in intramolecular.
3. the contact panel adhesive composite as described in above-mentioned 2, wherein, as above-mentioned (a1) composition and (a2) composition
In addition and there is the monomer of 1 olefinic double bond in intramolecular, above-mentioned monomer component can contain：(a3) more than 0.1 mass %
And the 7 nitrogenous monomer below mass %；More than (a4) 0 mass % and below 10 mass %, (a1) composition, (a2) composition
And beyond (a3) composition and there is monomer (here, (a1) composition+(a2) composition+(a3) of 1 olefinic double bond in intramolecular
Composition+(a4) composition=100 mass %).
4. the contact panel adhesive sheet of a mode of the invention, it has in a face or two faces of supporter
Contact panel adhesive composite any one of above-mentioned 1 to 3.
5. the laminated body of a mode of the invention includes：The first base material, the second base material and by any in above-mentioned 1 to 3
The bond layer that contact panel adhesive composite described in is obtained；Above-mentioned the first base material and above-mentioned second base material are via upper
Bond layer laminating is stated, glass or resin are contained respectively in above-mentioned the first base material and the second base material system.
The effect of invention
During using the contact panel adhesive composite of above-mentioned 1 to 3, containing above-mentioned (A) acrylic acid series polymeric compounds and
Above-mentioned (B) crosslinking agent, above-mentioned (A) acrylic acid is that polymer system contains (a1) (methyl) alkyl acrylate and (a2) hydroxyl
The copolymer of the monomer component of monomer, relative to the above-mentioned mass parts of (A) acrylic acid series polymeric compounds 100, containing 0.04 mass parts with
Above-mentioned (B) crosslinking agent below upper and 10 mass parts, thus, due to the structure of (B) crosslinking agent, can form elasticity bonding high
Oxidant layer.Thereby, it is possible to suppress to produce gas by supporter or adherend (below, being also referred to as in the present invention " base material "), and
And can suppress be derived from the reaction of (B) crosslinking agent and produce gas.Therefore, by using above-mentioned adhesive composite, can
Obtain it is a kind of can suppress under wet heat condition foaming and the transparency, bonding force, durability and conducting film non-aggressive are excellent
Bond layer.
Above-mentioned adhesive sheet is obtained by the contact panel of above-mentioned 1 to 3 with adhesive composite, therefore, it is possible to suppress
Foaming under wet heat condition, and the transparency, bonding force, durability and conducting film non-aggressive are excellent.
Above-mentioned laminated body by containing the bond layer that is obtained by the contact panel adhesive composite of above-mentioned 1 to 3,
The bond layer has excellent elasticity due to the structure of above-mentioned (B) crosslinking agent.Thus, the bond layer can make from first
The gas that base material and the second base material are produced is escaped, and can suppress to be derived from the gas that (B) crosslinking agent reacts and produces.Therefore,
The laminated body can suppress foaming under wet heat condition, and the transparency is excellent, and high adhesion due to the bond layer and resistance to
Long property, is not susceptible to peel off between the bond layer and the first base material and the second base material.
Brief description of the drawings
Fig. 1 is the profile of the laminated body for schematically showing an embodiment of the invention.
Specific embodiment
Hereinafter, on one side referring to the drawings, while explaining the present invention.Additionally, in the present invention, as long as no especially saying
Bright, " part " refers to " mass parts ", and " % " refers to " quality % ".
1. contact panel adhesive composite
The contact panel of an embodiment of the invention (below, is also simply recited as " viscous sometimes with adhesive composite
Connect agent composition ") contain：Weight average molecular weight is 100,000 less than 800,000 and contains substantially no the third of acidic-group
Olefin(e) acid based polymer (A) (below, is also simply recited as " (A) composition ") sometimes；With with following formulas (1) or following formulas (2)
Shown crosslinking agent (B) (below, being also simply recited as sometimes " (B) composition ").
(in formula, R1A、R1B、R1CIt independently is containing shown in the group shown in following formulas (3) and/or following formulas (4)
Group group, R2A、R2B、R2CIt is-(CH2)6- shown group.)
(in formula, R1A、R1B、R1CIt independently is containing shown in the group shown in following formulas (3) and/or following formulas (4)
Group group, R2A、R2B、R2C、R3A、R3B、R3C、R3D、R3E、R3FIt is-(CH2)6- shown group.)
(in formula, x is more than 2 and less than 10 integer, and m is more than 1 and less than 10 integer.)
(in formula, X represents singly-bound or-O-, and y is more than 2 and less than 10 integer, and n is more than 1 and less than 10 integer.)
1.1. (A) composition
(A) composition (below, is also simply recited as sometimes " (a1) composition ") containing (a1) (methyl) alkyl acrylate
The copolymer of the monomer component of the monomer (below, being also simply recited as sometimes " (a2) composition ") of (a2) hydroxyl.(a1) into
Divide and (a2) composition does not preferably have acidic-group.
In the present invention, so-called " acrylic acid series polymeric compounds " are to be selected from propylene containing more than 50 mass % in Component units
At least a kind in acid, acrylates, acrylate, methacrylic acid, methacrylate and methacrylate of polymerization
Thing.
(A) composition contains substantially no acidic-group.Here, so-called (A) composition refers to without acidic-group：Above-mentioned
In monomer component, the content of the monomer with acidic-group is below 0.5 mass % (preferably 0 mass %), preferably above-mentioned
Do not coordinate the monomer with acidic-group in monomer component intentionally.More specifically, do not have acidic-group in (A) composition
When, the acid value of (A) composition is usually below 0.5mg/KOH.Acidic-group, Neng Goufang are contained substantially no by making (A) composition
The only corrosion of the conducting film contained by contact panel." acidic-group " no restriction in the present invention, for example, carboxylic can be enumerated
Base, sulphur epoxide (sulfoxyl), cyano group.
Relative to the mass parts of adhesive composite 100 of present embodiment, the adhesive composite of present embodiment (will be molten
Agent remove after solids content) in the content of (A) composition can be for more than 90 mass parts and below 99.9 mass parts.
Can suppress from the elasticity that can be more reliably maintained under wet heat condition and further the hair under wet heat condition
From the viewpoint of bubble, in the adhesive composite of present embodiment, above-mentioned monomer component can containing more than 45 mass % and
(a1) composition of below 99 mass % (preferably more than 62 mass % and below 98 mass %)；With more than 1 mass % and 40 matter
(a2) composition of amount below % (preferably below the mass % of more than 2 mass % 30) is (here, by the monomer total amount in monomer component
It is set to 100 mass %).Now, (a1) composition in above-mentioned monomer component is preferably 85 matter with the total amount of (a2) composition
Amount more than % and below 100 mass %.In addition, above-mentioned monomer component can also further contain more than 0 mass % and 15 matter
It is beyond amount below %, (a1) composition and (a2) composition and there is 1 monomer of olefinic double bond in intramolecular.
It is so-called to suppress under wet heat condition in the bond layer obtained by the adhesive composite of present embodiment
Foaming refer to：For example in the car, have in the use under the high temperature and/or super-humid conditions in outdoor, steam bath-room, bathroom etc. resistance to
Long property.Particularly, the board-like image display of carrying touch surface is envisioned for being used under environment of all kinds, therefore,
The bond layer obtained by the adhesive composite of present embodiment, due to foaming when being used under wet heat condition can be suppressed
And be useful with bonding force, durability, the transparency and conducting film non-aggressive.
1.1.1. (a1) composition
(a1) composition can aid in the bonding force of the adhesive composite of present embodiment.(a1) composition for example can be with
Following formulas (5) is represented.
(in formula, R1Represent hydrogen atom or methyl, R2Represent alkyl or aralkyl.)
In above-mentioned formula (5), as R2Shown alkyl, can be straight-chain or branched, for example, carbon can be enumerated
Atomicity more than 1 and less than 18 alkyl (for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group,
N-pentyl, isopentyl, neopentyl, tertiary pentyl, 2- methyl butyls, 1- methyl butyls, n-hexyl, isohesyl, 3- methyl amyls, 2-
Methyl amyl, 1- methyl amyls, n-heptyl, n-octyl, iso-octyl, 2- ethylhexyls, n-nonyl, positive decyl, isodecyl, positive ten
One base, positive dodecyl (lauryl), positive tritriacontyl, positive tetradecyl (myristyl), different myristyl, positive palmityl (palm
Base), positive octadecyl (stearyl), isostearoyl base etc..
In addition, in above-mentioned formula (5), so-called " aralkyl (aralkyl group) " refers to a hydrogen atom of alkyl
The alkyl being substituted with aryl.In above-mentioned formula (5), as R2Shown aralkyl, can enumerate carbon number more than 1 and 18
Following aralkyl (for example, benzyl (phenyl methyl), phenethyl (phenylethyl)).
(a1) composition using a kind or can be applied in combination two or more.Wherein, above-mentioned monomer component, in order to better
Ground keeps bonding force, preferably in monomer component containing more than 35 mass % and below (preferably) 99 mass % selected from propylene
It is one kind or two or more in sour 2- Octyl Nitrites, 2-Ethylhexyl Methacrylate and n-butyl acrylate.
1.1.2. (a2) composition
(a2) composition can aid in and be reacted with (B) composition and form cross-linked structure.More specifically, contained by (a2) composition
Some hydroxyls are reacted with the NCO in (B) composition, thereby, it is possible to form cross-linked structure.
As (a2) composition, for example, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, propylene can be enumerated
Sour 2- hydroxypropyl acrylates, methacrylic acid 2- hydroxypropyl acrylates, acrylic acid 4- hydroxybutyls, methacrylic acid 4- hydroxybutyls, acrylic acid 2-
Hydroxyl -3- chlorine propyl ester, methacrylic acid 2- hydroxyl -3- chlorine propyl ester, acrylic acid 2- hydroxyl -3- phenoxy-propyls, methacrylic acid
(methyl) acrylate of hydroxyl of 2- hydroxyl -3- phenoxy-propyls etc. etc., wherein, using a kind or 2 kinds can be applied in combination
More than.Wherein, as (a2) composition, (methyl) acrylate of carbon number more than 1 and less than 6 hydroxyl is preferably used.
1.1.3. (a3) composition
In above-mentioned monomer component, as it is beyond (a1) composition and (a2) composition and intramolecular have 1 olefinic double bond
Monomer, (a3) that can be further containing more than 0 mass % and below 7 mass % nitrogenous monomer is (below, sometimes also simple
It is recited as " (a3) composition ").
As (a3) composition, for example, acrylic acid N can be enumerated, TMSDMA N dimethylamine base ethyl ester, methacrylic acid N, TMSDMA N dimethylamine
Base ethyl ester, methacrylic acid N, TMSDEA N diethylamine base ethyl ester, acrylamide, N, TMSDMA N dimethylamine base propylacrylamide, diacetone third
Acrylamide, acryloyl morpholine, wherein, using a kind or two or more can be applied in combination.Wherein, from the efficiency for forming cross-linked structure
From the aspect of excellent, (a3) composition is preferably acrylamide.
In order to more reliably suppressing the foaming under wet heat condition and obtaining the more excellent bond layer of durability,
The content of (a3) composition in above-mentioned monomer component is preferably more than 0 mass % and below 5 mass %, preferably 0.1 mass %
More than, more preferably more than 0.2 mass %, on the other hand, preferably below 4 mass %.
1.1.4. (a4) composition
In addition, for the polymer that obtains (A) composition above-mentioned monomer component can further contain (a4) 0 mass % with
There is 1 olefinic double bond beyond upper and below 10 mass %, (a1) composition, (a2) composition and (a3) composition and in intramolecular
Monomer (below, being also simply recited as sometimes " (a4) composition ").It should be noted that in this manual, (a1) composition+
(a2) composition+(a3) composition+(a4) composition=100 mass %.That is, (A) composition can be containing (a1) composition, (a2) composition,
And (a3) composition and/or the copolymer of the monomer component of (a4) composition as needed.
As (a4) composition, for example, can enumerate vinyl acetate, styrene, acrylonitrile, by vinyl polymerization
In monomer end there is macromonomer class, (methyl) acrylic acid, itaconic acid, maleic acid of free-radical polymerised vinyl etc. to have
There is monomer of carboxyl etc..The corrosion of conducting film is prevented to adjust the acid value of (A) composition, (a4) in above-mentioned monomer component into
The content divided is preferably more than 0 mass % and below 0.2 mass %.
1.1.5.Tg
From from the viewpoint of can more reliably realize good cementability and durability and reduction light leak, in this implementation
In the adhesive composite of mode, the Tg of (A) composition be preferably more than -80 DEG C and less than 20 DEG C, more preferably more than -80 DEG C and
Less than 0 DEG C.It should be noted that in the present invention, the Tg of (A) composition is the value calculated by following formula (6) (formula of FOX).
1/TgA=Wa1/Tga1+Wa2/Tga2+Wa3/Tga3+Wa4/Tga4…(6)
(in formula, TgARepresent the glass transition temperature (K) of (A) composition, Tga1、Tga2、Tga3、Tga4Represent respectively by structure
The glass transition temperature (Tg (K)) of the homopolymers prepared into monomer (a1), (a2), (a3), (a4), Wa1、Wa2、Wa3、Wa4Respectively
Represent (a1) composition, (a2) composition, (a3) composition, the weight fraction of (a4) composition contained in (A) composition).
Additionally, according to above-mentioned formula (6), TgACalculated as absolute temperature (K), therefore, can be converted into as needed Celsius
Temperature (DEG C).
In addition, the glass transition temperature of the homopolymers prepared by representational monomer is as described in Table 1, it is more specific and
Speech, for example, being documented in polymer handbook the 4th edition (Polymer Handbook Fourth Edition, Wiley-
Interscience, 1999) etc. in.
[table 1]
| Monomer | Tg(℃) | Monomer | Tg(℃) |
| Methyl acrylate | 8 | Methyl methacrylate | 105 |
| Ethyl acrylate | -24 | EMA | 65 |
| N-propyl | 3 | N propyl methacrylate | 35 |
| Isopropyl acrylate | -3 | Isopropyl methacrylate | 81 |
| N-butyl acrylate | -50 | Tert-butyl Methacrylate | 118 |
| Isobutyl acrylate | -40 | N-BMA | 20 |
| Tert-butyl acrylate | 43 | Isobutyl methacrylate | 48 |
| Acrylic acid n-pentyl ester | 22 | N-amylmethacrylate | -5 |
| The just own ester of acrylic acid | -57 | The just own ester of methacrylic acid | -5 |
| N-octyl | -65 | N octyl methacrylate | -20 |
| Isooctyl acrylate monomer | -58 | EHMA | -45 |
| 2-EHA | -70 | 2-Ethylhexyl Methacrylate | -10 |
| The positive nonyl ester of acrylic acid | -58 | Isodecyl methacrylate | -41 |
| Lauryl acrylate | -3 | Lauryl methacrylate | -65 |
| Tetradecyl acrylate | 24 | Tetradecyl methylacrylate | -72 |
| Process Conditions of Cetane Acrylate | 35 | Hexadecyl metrhacrylate | 15 |
| Acrylic acid iso stearyl ester | -18 | ||
| Cyclohexyl acrylate | 19 | Cyclohexyl methacrylate | 65 |
| Isobornyl acrylate | 94 | Isobornyl methacrylate | 180 |
| Acrylate | -22 | Phenoxyethyl methacrylate | 54 |
| Benzyl acrylate | 6 | Benzyl methacrylate | 54 |
| Acrylic acid 2- naphthalene esters | 85 | ||
| Methoxyethyl acrylate | -50 | Methoxyethyl methacrylate | -16 |
| Ethoxyethyl acrylate | -50 | Ethoxyethyl methacrylates | 15 |
| Ethoxydiglycol acrylate | -70 | ||
| Acrylic acid | 106 | Methacrylic acid | 185 |
| Carboxyethyl acrylates | 37 | ||
| Maleic acid | 130 | Itaconic acid | 100 |
| Acrylic acid 2- hydroxy methacrylates | -15 | 2-hydroxyethyl methacrylate | 55 |
| Acrylic acid 2- hydroxy propyl esters | -7 | Methacrylic acid 2- hydroxy propyl esters | 26 |
| Acrylic acid 4- hydroxy propyl esters | -30 | ||
| Methacrylic acid N, TMSDMA N dimethylamine base ethyl ester | 18 | ||
| Methacrylic acid N, TMSDEA N diethylamine base ethyl ester | 20 | ||
| Acrylamide | 153 | N, N- dimethyl ethyl acrylamide | 119 |
| N, TMSDMA N dimethylamine base propylacrylamide | 134 | ||
| Acrylonitrile | 125 | Styrene | 105 |
| Vinyl acetate | 30 |
1.1.7. weight average molecular weight (Mw)
In addition, from from the viewpoint of can more reliably realize good cementability and durability, present embodiment it is viscous
Connect in agent composition, the weight average molecular weight (Mw) of (A) composition is preferably more than 50,000 and less than 750,000, more preferably more than 100,000,
More preferably more than 150,000, on the other hand, preferably less than 600,000, more preferably less than 500,000, more preferably 40
Less than ten thousand.Here, the weight average molecular weight of (A) composition is to use GPC (gel permeation chromatography), and mark is asked under conditions of following
The weight average molecular weight (Mw) of quasi- polystyrene conversion.
<GPC condition determinations>
Determine device：HLC-8120GPC (TOSOH company systems)
GPC posts are constituted：Following 5 pedestals (whole TOSOH company systems)
(1) TSK-GEL HXL-H (guard column)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
Sample solution concentration：1.0mg/cm is diluted to using tetrahydrofuran3
Mobile phase solvent：Tetrahydrofuran
Flow：1.0cm3/ minute
Column temperature：40℃
1.2. (B) composition
As described above, in the adhesive composite of present embodiment, the crosslinking agent as (B) composition contains above-mentioned formula
(1) crosslinking agent or shown in above-mentioned formula (2).
In the adhesive composite of present embodiment, from assigning more excellent bonding force and durability and can be more certain
Prevent light leak from the viewpoint of, as the R contained by above-mentioned formula (1) or above-mentioned formula (2)1A、R1B、R1C, it is above-mentioned logical
In group shown in formula (3), x be more preferably more than 2 and less than 10 integer (more preferably more than 4 and less than 8 it is whole
Number), m is more preferably more than 1 and less than 10 integer (more preferably more than 1 and less than 6 integers).
In addition, as the R contained by above-mentioned formula (1) or above-mentioned formula (2)1A、R1B、R1C, above-mentioned formula (4) institute
The group for showing, y is more preferably more than 2 and less than 10 integer, more preferably 4~8 integer, n be more preferably more than 1 and
Less than 10 integer, more preferably less than 1 and less than 6 integer.In addition, in above-mentioned formula (1) and above-mentioned formula (2)
In, R1A、R1B、R1CCan be with identical, or can also be different, or multiple combinations.
(B) composition is isocyanates system crosslinking agent, more specifically, for example above-mentioned formula (1) of (B) composition or above-mentioned formula
(2) shown in, with the skeleton (- (O-CH from trimethylolpropane2-)3-C-CH2CH3) and isocyanates (- N=C=O)
Base.
From from the viewpoint of appropriate elasticity can be assigned to the adhesive composite of present embodiment, on (B) composition,
For example, the degree of cross linking (quantity of contained NCO in (B) composition of 1 molecule) can be more than 1 and less than 9, crosslinking
Degree is preferably more than 3 and less than 6.(B) composition for example can be by making trimethylolpropane with the carboxylic acid halides with NCO
(or ester or carboxylic acid) is condensed to obtain.
In the adhesive composite of present embodiment, from from the viewpoint of can further improve elasticity, (B) composition
Molecular weight is preferably more than 500 and 10, less than 000, more preferably 2, more than 000 and 7, less than 000.
In this regard, the adhesive composite of present embodiment is by containing (B) composition, due to above-mentioned contained by (B) composition
Group shown in group and/or above-mentioned formula (4) shown in formula (3) is (straight with what the skeleton from trimethylolpropane was abutted
Chain structure is (with R in above-mentioned formula (1) and above-mentioned formula (2)1A、R1B、R1CRepresent)), it is possible to increase the adhesive composite
Elasticity.Thereby, it is possible to the gas that the base material (such as glass and makrolon) suppressed by being fitted with the bond layer is produced.Separately
Outward, (B) composition is high to the stability of water and hydroxyl, therefore, the functional group reactionses of (B) composition and water and hydroxyl etc. and cause,
The gas (such as carbon dioxide, vapor, monomer, accessory substance etc.) produced by bond layer is few.
So, the bond layer for being obtained by the adhesive composite of present embodiment can suppress the gas produced by base material
Body, and it is few by gas that the bond layer is produced in itself, therefore, it is possible to suppress the foaming under wet heat condition.
From from the viewpoint of suppressing foaming and can improve bonding force and durability, the bonding agent group on present embodiment
The content of (B) composition of compound, relative to the mass parts of (A) composition 100 of present embodiment, it is more than preferably 0.04 mass parts and
Below 10 mass parts, more than more preferably 0.05 mass parts and below 10 mass parts, it is more than more preferably 0.06 mass parts,
More than particularly preferably 0.07 mass parts, on the other hand, below preferably 2 mass parts.
As (B) composition, commercially available crosslinking agent can be used.For example, as (B) composition, D-94 (sale can be used
Business：Soken Chemical ＆ Engineering Co., Ltd.), E405-70B (retailers：Asahi Kasei Corporation), MFA-75B (retailers：Asahi Chemical Industry's strain
Formula commercial firm) etc..
With without the crosslinking agent using above-mentioned formula (1) or above-mentioned formula (2) (for example, as commercially available isocyanates system
L-45 (the retailers of crosslinking agent：Soken Chemical ＆ Engineering Co., Ltd.), CORONATE HL (retailers：Japanese POLYURETHANE plants of formula
Commercial firm) etc.) compare, using present embodiment contact panel adhesive composite when, by containing above-mentioned formula (1) or on
(B) crosslinking agent shown in formula (2) is stated, elasticity is high, it is thus possible to suppress foaming.
As (B) crosslinking agent, for example, the crosslinking agent 1 to 3 described in embodiment described later can be enumerated.
1.3. other compositions
1.3.1. (C) silane coupling agent
The adhesive composite of present embodiment can contain beyond (A) composition and (B) composition as needed and further
Composition.For example, in the adhesive composite of present embodiment, it is also possible to coordinate not damaging in the range of effect of the invention
(C) silane coupling agent (below, being also simply recited as sometimes " (C) composition "), (D) ionic compound are (below, sometimes also simple
Be recited as " (D) composition "), antioxidant, ultra-violet absorber, tackifiers, plasticiser etc..
(C) composition for example can be vinyltrimethoxy silane, VTES and methacryloxypropyl
The silicon compound containing polymerism unsaturated group of base propyl trimethoxy silicane etc.；3- glycidoxypropyl group trimethoxy silicon
Alkane, 3- glycidoxypropyls dimethoxysilane and 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane etc. have
The silicon compound of epoxy construction；3- TSL 8330s, N- (2- aminoethyls) 3- TSL 8330s
With the silicon compound containing amido of N- (2- aminoethyls) -3- amino propyl methyl dimethoxysilanes etc.；And 3- chloropropyls
Trimethoxy silane；Oligomer type silane coupling agent etc., wherein, from not allowing to be also easy to produce for peeling under hygrothermal environment, preferably
Silane coupling agent with the functional group reacted with functional group contained in (A) composition.
When coordinating (C) composition in the adhesive composite of present embodiment, relative to the mass parts of (A) composition 100, (C)
The content of composition can be for more than 0.01 mass parts and below 0.5 mass parts, more than preferably 0.05 mass parts and 0.3 mass parts
Below.
1.3.2. (D) ionic compound
In addition, the adhesive composite of present embodiment can also contain (D) ionic compound.As (D) composition, example
Such as, can enumerate that be made up of anion and cation is liquid or solid-like ionic compound at 25 DEG C, it is specific and
Speech, can enumerate alkali metal salt, ionic liquid (being liquid at 25 DEG C), surfactant etc..
Relative to the mass parts of (A) composition 100 of present embodiment, (D) in the adhesive composite of present embodiment into
The content divided can be more than 0.01 mass parts below 3 mass parts, more than preferably 0.05 mass parts and below 2.5 mass parts.
1.4. the polymerization of (A) composition
(A) polymerization of composition is not particularly limited, and can use polymerisation in solution, emulsion polymerization, suspension polymerisation etc.
Known method is polymerized, when adhesive composite of the invention is manufactured using the mixture of the copolymer that is obtained by polymerization,
It is fairly simple and from the viewpoint of being carried out with the short time from process step, preferably it is polymerized by polymerisation in solution.
Polymerisation in solution in polymerization tank generally by adding regulation organic solvent, each monomer, polymerization initiator and according to need
Chain-transferring agent wanted and use etc., makes its heating response number small while stirring under the reflux temperature of stream of nitrogen gas or organic solvent
When come carry out.
In addition, at this time it is also possible to gradually adding at least a portion of organic solvent, monomer and/or polymerization initiator.As
Organic solvent, can enumerate：For example benzene, toluene, ethylbenzene, n-proplbenzene, 2-methyl-2-phenylpropane, ortho-xylene, meta-xylene, paraxylene,
Tetrahydronaphthalene, decahydronaphthalenes, aromatic base crude oil brain etc. it is aromatic hydrocarbon；For example n-hexane, normal heptane, normal octane, isooctane,
The fatty series or alicyclic ring family hydro carbons of n-decane, cinene, Mineral spirits, naphtha, turpentine oil etc.；Such as ethyl acetate, acetic acid
N-butyl, n-amyl acetate, acetic acid 2- hydroxy methacrylates, acetic acid 2- butoxyethyls, acetic acid 3- methoxybutyls, methyl benzoate
Deng esters；Such as ketone of acetone, MEK, methyl iso-butyl ketone (MIBK), isophorone, cyclohexanone, methyl cyclohexanone etc.；For example
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol
The glycol ethers of monobutyl ether etc.；Such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol class
Deng alcohols etc..These organic solvents can individually using or mix two or more and use.
Among these polymerization organic solvents, in the polymerization of (A) composition, preferably use and be not easy in the polymerization product
In terms of the organic solvent of raw chain tra nsfer, such as esters, ketone, dissolubility, polymerisation easiness particularly from (A) composition etc.
Consider, preferably use ethyl acetate, MEK, acetone etc..
As above-mentioned polymerization initiator, organic peroxide, the idol that can be used in common polymerisation in solution can be used
Nitrogen compound etc..As such organic peroxide, for example, can enumerate TBHP, isopropyl benzene hydroperoxide,
Cumyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxidating hexanoyl, di-isopropyl peroxydicarbonate, peroxide
Double (the 4,4- di-tert-butyl peroxides cyclohexyl) propane of change carbonic acid two -2- Octyl Nitrites, the peroxidating pivalic acid tert-butyl ester, 2,2-,
Double (the t-amyl peroxy cyclohexyl of the 4,4- bis-) propane of 2,2-, 2,2- double (the t-octyl peroxidating cyclohexyl of 4,4- bis-) propane, 2,
Double (the 4,4- di-tert-butyl peroxides cyclohexyl) butane of the double (- α of the 4,4- bis--cumyl peroxy cyclohexyl) propane of 2-, 2,2-,
2,2- double (4,4- bis- t-octyl peroxidating cyclohexyl) butane etc., as azo-compound, for example, can enumerate 2,2 '-azo
Double -2,4- the methyl pentane nitriles of double-isobutyronitrile, 2,2 '-azo, the double -4- methoxyl group -2,4- methyl pentane nitriles of 2,2 '-azo etc..
Among these polymerization initiators, the polymerization of graft reaction is not preferably produced to trigger in the polymerisation of (A) composition
Agent, particularly preferred azo system polymerization initiator.100 mass parts, its usage amount are added up to be usually 0.01 mass parts relative to monomer
Above and below 2 mass parts, more than preferably 0.1 mass parts and below 1.0 mass parts.
In addition, when (A) composition contained by adhesive composite of the invention is manufactured, generally system does not use chain tra nsfer
Agent, but also chain-transferring agent can be as needed used in the range of the purpose of the present invention and effect not damaging.
As such chain-transferring agent, for example, cyanoacetic acid can be enumerated；The carbon number more than 1 of cyanoacetic acid and less than 8
Alkyl esters；Bromoacetic acid；The carbon number more than 1 and less than 8 alkyl esters of bromoacetic acid；Anthracene, phenanthrene, fluorenes, 9- phenyl fluorenes etc.
Aromatic compound species；Paranitroanilinum, nitrobenzene, dinitro benzene, paranitrobenzoic acid, p-nitrophenol, para-nitrotoluene
Deng aromatic nitro compound class；The quinone derivatives class of benzoquinones, 2,3,5,6- tetramethyls -1,4-benzoquinone etc.；Tetrabutyl borine
Deng borane derivative；Carbon tetrabromide, carbon tetrachloride, 1,1,2,2- tetrabromoethanes, tribromo-ethylene, trichloro ethylene, the chloromethane of bromine three
The halogenated hydrocarbons of the chloro- 1- propane of alkane, bromoform, 3- etc.；The aldehydes of chloral, furfural etc.：Carbon number more than 1 and less than 18
Alkyl sulfide alcohols；The aromatic mercaptans class of benzenethiol, toluenethiol etc.；TGA, the carbon number more than 1 of TGA and
Less than 10 alkyl esters；Carbon number more than 1 and less than 12 hydroxyalkylmercaptan class；The terpenes of firpene, terpinolene etc.
Deng.
As the polymerization temperature of (A) composition, typically about more than 30 DEG C and less than 180 DEG C, preferably more than 40 DEG C and 150
Below DEG C, it is preferably more than 50 DEG C and less than 90 DEG C of scope.Additionally, containing in the polymer obtained by solution polymerization process etc.
When having unreacted monomer, in order to remove the monomer, it is also possible to refined by using the reprecipitation method of methyl alcohol etc..
1.5. the manufacture of adhesive composite
The adhesive composite of present embodiment usually can be by above-mentioned (A) composition, (B) composition and as needed any
Composition is mixed simultaneously or according to arbitrary order and to be prepared.In addition, when (A) composition is mixed with (B) composition, by molten
In the case that liquid polymerization prepares (A) composition, (B) composition is added in the solution of (A) composition that can be after the completion of containing polymerization,
In the case of preparing (A) composition by bulk polymerization, due to that can become to be difficult to uniform mixing after completion of polymerization, therefore preferably exist
Mixing (B) composition is added in the way of the polymerization.
1.6. purposes and action effect
The bonding agent that the adhesive composite of present embodiment can be suitable as contact panel is used.Using this implementation
During the adhesive composite of mode, excellent durability can be played under wet heat condition, and for as base material (example
Such as glass or resin) adherend bonding when, the foaming in the bond layer can be suppressed under wet heat condition.
The reason for foaming in bond layer, mainly thinks there are two.First reason is in the base fitted with bond layer
The gas that material is produced.Second reason is due to the gas of the composition for constituting bond layer.
First, as the gas from base material of first reason be, for example, by makrolon, polymethyl methacrylate,
The gas that the organic material (resin) of polyimides etc. is produced.
For example, for the characteristic in material, makrolon is known to produce exhaust (CO under the high temperature conditions2).In addition, poly-
Carbonic ester easily makes vapor (H2O) pass through, particularly under the high temperature conditions, the transmission of vapor is notable.Due to these gases,
Sometimes foaming is produced in the bond layer fitted with makrolon.In addition, during for polymethyl methacrylate, it is vapor, not anti-
The monomer answered is produced as gas sometimes.
It is due to contained by adhesive composite as the gas of the composition for constituting bond layer of resulting from of second reason
The gas that some compositions react and produce.For example, during isocyanates system crosslinking agent, NCO and water react and
Sometimes carbon dioxide is produced.
In this regard, it is yes to prevent characteristics inference as the foaming of an action effect of the adhesive composite of present embodiment
Due to obtained from following mechanism of action.
That is, using the adhesive composite of present embodiment when substrate surface sets bond layer, by making the bonding
Agent composition have (B) composition, due to contained by (B) composition with the group and/or above-mentioned formula shown in above-mentioned formula (1)
(2) group shown in, makes elastic raising, as a result, can suppress the gas produced by base material.In addition, in the viscous of present embodiment
Connect in agent composition, the gas for being reacted with (B) composition and being produced is few.According to the above, the bonding agent of present embodiment is used
When composition forms the bond layer for the component for constituting contact panel of fitting, the foaming of the bond layer can be suppressed, and
And the bonding force and durability (wet heat durability) of the bond layer are excellent, therefore, fitted using the bond layer and constitute touch-control
During the component of panel, it is not easy to produce peeling.And, the adhesive composite of present embodiment does not contain sour composition, therefore leads
Electrolemma non-aggressive is excellent.
2. adhesive sheet
The adhesive sheet (bond layer) of another embodiment of the invention is in a face of supporter or two masks
There is the bond layer of the contact panel adhesive composite containing above-mentioned implementation method.
When the adhesive sheet of present embodiment is manufactured, above-mentioned bond layer can be by using gravure coater, Meyer
Above-mentioned adhesive composite is coated on supporter by family name's rod (Mayer ' s bar) coating machine, pneumatic doctor knife coater, roll-coater etc.
On, adhesive composite on adhesive sheet will be coated it is dried in normal temperature or by heating and is crosslinked and is formed, or
Bond layer can also be arranged on stripping film, be transferred to adherend to be formed.
In addition, the thickness on adhesive sheet, generally, dries thickness for more than 10 μm and less than 1000 μm, preferably 25 μm
Above and less than 500 μm Zuo You.Additionally, the use in adhesive sheet is preceding, in order to protect bond layer, it is also possible in the bonding agent
The surface stack stripping film of layer.
Supporter can for example enumerate makrolon, polymethyl methacrylate, polyethylene terephthalate (PET)
Deng polyester, cellulose triacetate (TAC), polysulfones, polyimides, polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride
Deng organic polymer and glass.
Adherend can enumerate the glass with conductive film layer or the resin film with conducting film, makrolon, poly- first
The polyester of base methyl acrylate, polyethylene terephthalate (PET) etc., cellulose triacetate (TAC), polysulfones, polyamides are sub-
Organic polymer and glass of amine, polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride etc. etc..
The thickness of above-mentioned supporter or adherend (base material) is not particularly limited, when being organic polymer, for example, it is preferable to
It is more than 12 μm and less than 75 μm.Additionally, above-mentioned base material can also have any one form of individual layer and multilayer.In addition, in base
Material surface, for example, it is also possible to implement the chemistry of the physical treatment of Corona discharge Treatment, corona treatment etc., primary coat treatment etc.
The known usual surface treatments such as treatment.During for glass, preferably more than 25 μm and less than 2000 μm.
3. laminated body
As shown in figure 1, the laminated body 100 of an embodiment of the invention includes the first base material 20, the and of the second base material 30
Bond layer 10, the first base material 20 is fitted with the second base material 30 via bond layer 10.
The laminated body of present embodiment can be by via the bonding agent group of the contact panel as described in above-mentioned implementation method
Operation that the bond layer that compound is obtained fits the first base material with the second base material is obtained.
More specifically, the adhesive sheet by will be obtained by the contact panel adhesive composite of above-mentioned implementation method
(bond layer 10) is attached at the base material 30 of the first base material 20 or second, can configure the base material 30 of the first base material 20 and second it
Between.That is, the surface of bond layer 10 is attached to after the surface of either one of the base material 30 of the first base material 20 or second, this is glued
Connect oxidant layer 10 another surface (back side) be attached to the second base material 30 or the first base material 20 the opposing party surface, thus, energy
The first base material 20 is fitted with the second base material 30 using bond layer 10 enough.
The base material 20 of the first base material 10 and second is able to contain glass or resin.Can be first as an example
Base material 10 contains glass, and the second base material 20 contains resin.
As the resin for constituting the base material 20 of the first base material 10 and/or second, for example, can enumerate as supporter above-mentioned
Illustrated organic polymer.By applying heat, moisture, the resin as contained by the resin are produced from these resins sometimes
Gas, the monomer from the raw material as the resin, the gas of accessory substance for decomposing and producing.Bond layer 10 is by this implementation
What the adhesive composite of mode was obtained, its elasticity is high, therefore, it is possible to suppress to be produced from the base material 30 of the first base material 20 and/or second
Gas.
In the laminated body 100 of present embodiment, by via bond layer 10 fit the base material 30 of the first base material 20 and second,
Due to the elasticity of bond layer 10 so that bond layer 10 can suppress what is produced by the base material 30 of the first base material 20 and/or second
Gas, in addition, the gas produced by bond layer 10 itself is also few.Therefore, it is possible to suppress the foaming in bond layer 10.
Thus, bond layer 10 it is transparent excellent, also, using the excellent bond layer 10 of bonding force by the first base material 20 and second
Base material 30 is fitted, therefore, laminated body 100 is less likely to occur to peel off.
4. embodiment
Hereinafter, the present invention is illustrated based on following embodiments, but the present invention is not limited to embodiment.
4.1. the preparation of (A) composition
4.1.1. the preparation of polymer A, C to G
Possess have the reaction unit of mixer, reflux cooler, thermometer and nitrogen ingress pipe in addition have table 2 below
The monomer component of shown compounding ratio, then, adds ethyl acetate so that monomer concentration turns into the use level of 50 mass %.
Then, the mass parts of azobis isobutyronitrile 0.1 are added, while using the air in nitrogen displacement reaction vessel, while being stirred
And 60 DEG C are warming up to, its reaction 6 hours is made afterwards.After reaction terminates, diluted using ethyl acetate (solvent), obtain (A) composition
The solution of (acrylic acid series polymeric compounds A to E).Additionally, the acid value of acrylic acid series polymeric compounds A, C to F is 0mg/KOH.Acrylic acid
The acid value of based polymer G is 4mg/KOH.
4.1.2. the preparation of polymer B
Possess have the reaction unit of mixer, reflux cooler, thermometer and nitrogen ingress pipe in addition have table 2 below
The monomer component of shown compounding ratio, then, adds ethyl acetate so that monomer concentration turns into the use level of 40 mass %.
Then, the mass parts of azobis isobutyronitrile 0.1 are added, using the air in nitrogen displacement reaction vessel, is stirred for one time for one time
And 60 DEG C are warming up to, its reaction 6 hours is made afterwards.After reaction terminates, diluted using ethyl acetate (solvent), obtain (A) composition
The solution of (acrylic acid series polymeric compounds B).Additionally, the acid value of acrylic acid series polymeric compounds B is 0mg/KOH.
4.2. the preparation of adhesive composite and the making of evaluation adhesive sheet
Using (A) composition obtained in above-mentioned 4.1., according to Table 3 below cooperation (in table 3, the cooperation scale of each composition
Show the ratio in the solids content after removing solvent) each composition is added, obtain the bonding agent of embodiment 1 to 9 and comparative example 1 to 7
The solution of composition.
Then, by the surface of the polyester film by the solution coating of the adhesive composite after a stripping treatment and it is made
Dry, obtain the adhesive sheet of the bond layer with 50 μm of thickness.By the adhesive sheet under conditions of 23 DEG C/50%RH
Dark place cures 7 days afterwards, is attached to a face of the polyethylene terephthalate film of 100 μm of thickness, obtains evaluating and uses viscous
Contact pin material.
Additionally, as (B) composition, as described in Table 3, using crosslinking agent 1 to 3.Crosslinking agent 1 to 5 has following respectively
Structure of the structural formula (7) shown in (11).Additionally, the weight average molecular weight (MW) of crosslinking agent 1 is for about 4,000, the weight of crosslinking agent 2
Average molecular weight (MW) is for example for about 3,700, and the weight average molecular weight (MW) of crosslinking agent 3 is for example for about 4,000.
[crosslinking agent 1]
(in formula, l is more than 1 and less than 10, m are more than 1 and less than 10, n are more than 1 and less than 10.)
[crosslinking agent 2]
(in formula, l is more than 1 and less than 10, m are more than 1 and less than 10, n are more than 1 and less than 10, a are more than 1 and 10
Hereinafter, b is more than 1 and less than 10, c are more than 1 and less than 10.)
[crosslinking agent 3]
(in formula, l is more than 1 and less than 10, m are more than 1 and less than 10, n are more than 1 and less than 10.)
[crosslinking agent 4]
[crosslinking agent 5]
For each evaluation adhesive sheet, 180 ° of peeling forces and moisture-proof durability are evaluated (table 3) using following method.
4.3. evaluation method
4.3.1. 180 ° of peeling forces (bonding force)
The evaluation that will be obtained in above-mentioned 4.2 turns into 25mm × 150mm with adhesive sheet severing, by the stripping film stripping in face
Under, each adherend described in table 3 is attached at, carry out 3 pressure viscosity back and forth using the roller of weight 2kg.23 after pressure viscosity
DEG C × 50%RH atmosphere under place 20 minutes afterwards, peeling speed 300mm/ minutes in 180 ° of short sides of direction tensile test specimen and
Using the average value of the measured value of 10 times as peeling force.
4.3.2. moisture-proof durability
The evaluation that will be obtained in above-mentioned 4.2 turns into 50mm × 60mm with adhesive sheet severing, and the stripping film of side is peeled,
Each adherend described in table 3 is attached at, 3 pressure viscosity back and forth are carried out using the roller of weight 2kg.In 50 DEG C × 5atm after pressure viscosity
Carry out autoclave process 20 minutes.Then, it is being stored at room temperature 1 hour afterwards, is being placed 24 hours under 85 DEG C/85%RH environment,
1 hour is stood in 23 DEG C/50%RH afterwards, confirm whether there is the foaming of bond layer by visual observation.The benchmark of evaluation is as described below.
(evaluation)
○：Visually not confirm bubble in bond layer.
×：Visually to confirm air pocket in bond layer.Or bond layer floats from supporter or adherend.
4.3.3. conducting film non-aggressive
The evaluation that will be obtained in above-mentioned 4.2 turns into 10mm × 60mm with adhesive sheet severing, and the stripping film of side is peeled
And ITO evaporation PET film of the severing as 10mm × 100mm is attached at, carry out autoclave process 20 minutes in 50 DEG C × 5atm.Connect
, be stored at room temperature 1 hour afterwards, placed 500 hours in the environment of 60 DEG C and 90%RH, at 23 DEG C and humidity 65%RH
Under the conditions of stand 1 hour afterwards, determine ITO evaporation films resistance value, compare with the resistance value before the experiment of measured in advance, obtain
Relative to the rate of change of the resistance value of the resistance value before experiment.Additionally, using TESTER (three and electric meter in the measure of resistance value
Device (strain) system, DIGITAL MULTIMETER PC510).
(evaluation)
○：Rate of change relative to the resistance value of the resistance value before experiment is less than 115%
×：It is more than 115% relative to the rate of change of the resistance value of the resistance value before experiment
4.3.4. the mist degree of sheet material
After deaeration treatment, the adhesive composite of embodiment 1 to 9 and comparative example 1 to 7 is coated with using wing respectively
Polyethylene terephthalate film after the lift-off processing of 38 μm of thickness is (below：Barrier film) on, in 90 DEG C of dryings 3 minutes,
Form the film of 50 μm of dry film thickness.In the opposing face in the attaching face with above-mentioned polyethylene terephthalate film of film,
Further fit barrier film, the evaluation adhesive sheet of the bond layer for obtaining there is 50 μm of the thickness clamped by 2 barrier films.Connect
, the barrier film in a face of the above-mentioned evaluation adhesive sheet that the method recorded by this column is obtained is peeled off, and fits in 1.0mm
Thick slide, the barrier film in another face of adhesive sheet is peeled off, and using haze meter HM-150, (color skill is studied in village
Institute) determine the mist degree for there was only bond layer.
[table 2]
[table 3]
Additionally, being abbreviated as the following meaning in table 2 and table 3.
AA：Acrylic acid
AM：Acrylamide
BA：N-butyl acrylate
2EHA：2-EHA
2EHMA：2-Ethylhexyl Methacrylate
MA：Methyl acrylate
HEA：Acrylic acid 2- hydroxy methacrylates
HEMA：2-hydroxyethyl methacrylate
ISTA：Acrylic acid iso stearyl ester
Result according to table 3 is it is understood that the composition of above-described embodiment 1 to 9 contains above-mentioned leading to by being used as (B) composition
The crosslinking agent 3 shown in crosslinking agent 1 or crosslinking agent 2 or above-mentioned formula (2) shown in formula (1), can suppress under wet heat condition
Foaming, and bonding force and excellent durability and the transparency high can be realized.
In contrast, it is understood that the composition of above-mentioned comparative example 1 to 6 as (B) composition due to not containing above-mentioned formula
(1) any one (that is, crosslinking for being used in comparative example 1 to 6 of the crosslinking agent shown in crosslinking agent and above-mentioned formula (2) shown in
Agent 4 and crosslinking agent 5 are without the structure shown in above-mentioned formula (1) or above-mentioned formula (2)), therefore, it is impossible to fully reduce hair
Bubble.In addition, comparative example 2 is the example that evaluation adhesive sheet is pasted with base material (makrolon), it is to be understood that using containing
The bonding force of the bond layer of the adhesive composite of crosslinking agent 4 is low.Further, it is to be understood that because the composition of comparative example 7 contains
There is the polymer G with acidic-group, therefore conducting film non-aggressive is poor.
In addition, in above-described embodiment 1 to 9, also further coordinate in addition to addition (A) composition and (B) composition (C) into
Divide 1 mass parts and the mass parts of (D) composition 0.1 and prepare adhesive composite, use the adhesive composite to manufacture adhesive sheet
When, in the same manner as the above results, the resulting adhesive sheet can suppress the foaming under wet heat condition, and with high
Bonding force and excellent durability and the transparency.
Symbol description
10 bond layers
20 the first base materials
30 second base materials
100 laminated bodies
Claims (5)
1. a kind of contact panel adhesive composite, it is characterised in that contain：
(A) weight average molecular weight is 100,000 less than 800,000 and contains substantially no the acrylic polymeric of acidic-group
Thing；With
(B) following formulas (1) or the crosslinking agent shown in following formulas (2),
(A) acrylic acid series polymeric compounds are the monomers of the monomer containing (a1) (methyl) alkyl acrylate He (a2) hydroxyl
The copolymer of composition,
Relative to the mass parts of (A) acrylic acid series polymeric compounds 100, contain the institute more than 0.04 mass parts and below 10 mass parts
(B) crosslinking agent is stated,
In formula (1), R1A、R1B、R1CIt independently is containing shown in the group shown in following formulas (3) and/or following formulas (4)
The group of group, R2A、R2B、R2CIt is-(CH2)6- shown group,
In formula (2), R1A、R1B、R1CIt independently is and contains the base shown in the base shown in following formulas (3) and/or following formulas (4)
The group of group, R2A、R2B、R2C、R3A、R3B、R3C、R3D、R3E、R3FIt is-(CH2)6- shown group,
In formula (3), x is more than 2 and less than 10 integer, and m is more than 1 and less than 10 integer,
In formula (4), X represents singly-bound or-O-, and y is more than 2 and less than 10 integer, and n is more than 1 and less than 10 integer.
2. contact panel adhesive composite as claimed in claim 1, it is characterised in that：
The monomer component contains：(a1) (methyl) alkyl acrylate of more than 45 mass % and below 99 mass %；1
The monomer of (a2) hydroxyl of more than quality % and 40 below mass %；With more than 0 mass % and below 15 mass %,
(a1) beyond composition and (a2) composition and there is 1 monomer of olefinic double bond in intramolecular.
3. contact panel adhesive composite as claimed in claim 2, it is characterised in that：
In the monomer component, as it is beyond (a1) composition and (a2) composition and intramolecular have 1 olefinic double bond
Monomer, also contain：
(a3) the nitrogenous monomer of more than 0.1 mass % and below 7 mass %；With
(a4) more than 0 mass % and below 10 mass %, it is beyond (a1) composition, (a2) composition and (a3) composition and point
There is 1 monomer of olefinic double bond in sub, wherein, (a1) composition+(a2) composition+(a3) composition+(a4) composition=100 matter
Amount %.
4. a kind of adhesive sheet, it is characterised in that：
In the contact panel bonding agent group that a face of supporter or two masks are had the right any one of requirement 1~3
Compound.
5. a kind of laminated body, it is characterised in that including：
The first base material,
Second base material and
The bond layer that contact panel adhesive composite as any one of claims 1 to 3 is obtained；
The first base material and second base material are fitted via the bond layer,
The first base material and the second base material contain glass or resin respectively.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-202849 | 2014-10-01 | ||
| JP2014202849 | 2014-10-01 | ||
| PCT/JP2015/076766 WO2016052276A1 (en) | 2014-10-01 | 2015-09-18 | Touch panel adhesive composition, adhesive sheet, and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106795406A true CN106795406A (en) | 2017-05-31 |
| CN106795406B CN106795406B (en) | 2019-02-19 |
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ID=55630316
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580053776.2A Active CN106795406B (en) | 2014-10-01 | 2015-09-18 | Touch panel adhesive composite, adhesive sheet and laminated body |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6334721B2 (en) |
| KR (1) | KR102116601B1 (en) |
| CN (1) | CN106795406B (en) |
| TW (1) | TWI664254B (en) |
| WO (1) | WO2016052276A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114207067A (en) * | 2019-08-09 | 2022-03-18 | 三菱瓦斯化学株式会社 | Adhesive sheet for bonding, multilayer body, and method for producing multilayer body |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6390661B2 (en) * | 2016-04-19 | 2018-09-19 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet |
| KR102603519B1 (en) | 2017-08-10 | 2023-11-17 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Laminate and touch panel |
| JP6443578B1 (en) * | 2017-09-29 | 2018-12-26 | 王子ホールディングス株式会社 | Adhesive composition, adhesive sheet and laminate |
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| CN101313043A (en) * | 2005-11-21 | 2008-11-26 | 综研化学株式会社 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| CN105073937A (en) * | 2013-04-01 | 2015-11-18 | 综研化学株式会社 | Adhesive agent composition for optical films, and adhesive optical film |
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| JPH1195012A (en) * | 1997-09-24 | 1999-04-09 | Nippon Kayaku Co Ltd | Light scattering film |
| KR101281643B1 (en) * | 2005-11-21 | 2013-07-03 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| JP4800363B2 (en) | 2008-09-26 | 2011-10-26 | 日東電工株式会社 | Adhesive sheet for bonding optical members |
| JP5255525B2 (en) * | 2009-06-15 | 2013-08-07 | 古河電気工業株式会社 | Adhesive tape for semiconductor wafer processing and manufacturing method thereof |
| JP5725760B2 (en) * | 2010-08-19 | 2015-05-27 | 大同化成工業株式会社 | Acrylic polymer compounds used in pressure-sensitive adhesive compositions for touch panels |
| JP6117478B2 (en) * | 2011-04-22 | 2017-04-19 | 日東電工株式会社 | Adhesive functional film and display device |
| JP2013253154A (en) * | 2012-06-06 | 2013-12-19 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and touch panel laminate |
| JP2014173065A (en) * | 2013-03-12 | 2014-09-22 | Nitto Denko Corp | Adhesive, adhesive layer, adhesive sheet, and touch panel |
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2015
- 2015-09-18 WO PCT/JP2015/076766 patent/WO2016052276A1/en active Application Filing
- 2015-09-18 JP JP2016551948A patent/JP6334721B2/en active Active
- 2015-09-18 CN CN201580053776.2A patent/CN106795406B/en active Active
- 2015-09-18 KR KR1020177008801A patent/KR102116601B1/en active IP Right Grant
- 2015-10-01 TW TW104132358A patent/TWI664254B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313043A (en) * | 2005-11-21 | 2008-11-26 | 综研化学株式会社 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| CN105073937A (en) * | 2013-04-01 | 2015-11-18 | 综研化学株式会社 | Adhesive agent composition for optical films, and adhesive optical film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114207067A (en) * | 2019-08-09 | 2022-03-18 | 三菱瓦斯化学株式会社 | Adhesive sheet for bonding, multilayer body, and method for producing multilayer body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016052276A1 (en) | 2017-07-20 |
| WO2016052276A1 (en) | 2016-04-07 |
| TW201619333A (en) | 2016-06-01 |
| CN106795406B (en) | 2019-02-19 |
| JP6334721B2 (en) | 2018-05-30 |
| TWI664254B (en) | 2019-07-01 |
| KR20170065521A (en) | 2017-06-13 |
| KR102116601B1 (en) | 2020-05-28 |
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