CN107835845A - Adhesive composition and surface protection film - Google Patents
Adhesive composition and surface protection film Download PDFInfo
- Publication number
- CN107835845A CN107835845A CN201680041066.2A CN201680041066A CN107835845A CN 107835845 A CN107835845 A CN 107835845A CN 201680041066 A CN201680041066 A CN 201680041066A CN 107835845 A CN107835845 A CN 107835845A
- Authority
- CN
- China
- Prior art keywords
- adhesive composition
- polyurethane
- mentioned
- mass parts
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
Abstract
Problem to be solved by this invention is to provide a kind of whitening resistance that can obtain under moisture-proof thermal environment and the adhesive composition to the excellent bonding epithelium of the stain resistance of adherend.The present invention provides a kind of adhesive composition, it is characterised in that contains the polyurethane (A) with more than 2 hydroxyls, crosslinking agent (B), carbodiimide compound (C) and organic solvent (D).In addition, the present invention provides a kind of surface protection film of the curing overlay film with above-mentioned adhesive composition.The adhesive composition of the present invention can be especially suitable for the adhesive layer of surface protection film.The adhesive composition of the present invention can obtain the whitening resistance under moisture-proof thermal environment and the excellent bonding epithelium of the stain resistance to adherend.
Description
Technical field
The present invention relates to the adhesive composition that can be suitable as surface protection film and use.
Background technology
For the purpose of the dirt on the surface for preventing glass, plastics etc., cut, surface protection film is widely utilized.
On the composition of above-mentioned surface protection film, such as use and be laminated with the plastics such as polyethylene terephthalate film
Film, adhesive phase, the surface protection film of mold release film (for example, referring to patent document 1).In addition, made as above-mentioned adhesive phase
Adhesive, silicone adhesive, acrylic adhesives, polyurethane binder etc. are make use of extensively.
Particularly in the manufacturing process of the touch panel surrounding member in for smart mobile phone, tablet personal computer, from stickup
Set out in terms of the efficiency of operation and the dominance of price, the utilization using the diaphragm of polyurethane binder is increasing.
However, in the case of using polyurethane series diaphragm, problems be present：During transportation process in manufacturing process, thereafter,
Under moisture-proof thermal environment during use etc., adherend is polluted, or albefaction occurs due to damp and hot.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-124293 publications
The content of the invention
Invent problem to be solved
Problem to be solved by this invention is to provide a kind of whitening resistance that can obtain under moisture-proof thermal environment and to quilt
Glue the excellent adhesive composition for bonding epithelium of the stain resistance of thing.
Means for solving the problems
The present invention provides a kind of adhesive composition, it is characterised in that contains：Polyurethane with more than 2 hydroxyls
(A), crosslinking agent (B), carbodiimide compound (C) and organic solvent (D).
In addition, the present invention provides a kind of surface protection film of the curing overlay film with above-mentioned adhesive composition.
Invention effect
The adhesive composition of the present invention can obtain whitening resistance under moisture-proof thermal environment and to the resistance to of adherend
The excellent bonding epithelium of contaminative.In addition, in the case where also containing specific carboxylate in making above-mentioned adhesive composition, remove
Outside the effect above, additionally it is possible to further improve under the wetability and moisture-proof thermal environment of adherend to the resistance to of adherend
Contaminative.Therefore, adhesive composition of the invention can be especially suitable for the adhesive layer of surface protection film.
Embodiment
The adhesive composition of the present invention contains the polyurethane (A) with more than 2 hydroxyls, crosslinking agent (B), carbodiimide
Compound (C) and organic solvent (D) are as required composition.
Above-mentioned polyurethane (A) has more than 2 hydroxyls being used for crosslinking agent described later (B) crosslinking, preferably with 4~8
The hydroxyl of individual scope.It is crosslinked by above-mentioned polyurethane (A) and crosslinking agent (B), so as to can obtain good bonding physical property, resistance to
Contaminative and whitening resistance.
As above-mentioned polyurethane (A), can use for example make polyalcohol (a ' 1) and polyisocyanates (a2) reacted and
The polyurethane obtained.
As above-mentioned polyalcohol (a ' 1), such as polyoxyalkylene polyol (a1), PEPA, poly- carbonic acid can be used
Ester polyol, polybutadiene polyol, polycaprolactone polyol, acrylpolyol, dimer diols, polyisoprene are more
First alcohol etc..These polyalcohols can be used alone, and can also use two or more.Among these materials, bonding is improved from further
The flexibility of agent assigns and from the viewpoint of the water-disintegrable stain resistance and whitening resistance of polyurethane, preferably uses
Polyoxyalkylene polyol (a1).
As above-mentioned polyoxyalkylene polyol (a1), can use for example polyoxyethylene polyols, polyoxypropylene polyol,
Polybutylene polyalcohol, polyoxyethylene polyoxypropylene polyalcohol, polyoxyethylene polybutylene polyalcohol, polyoxypropylene polybutylene
Polyalcohol etc..These polyoxyalkylene polyols can be used alone, and can also use two or more.In addition, as above-mentioned polyoxygenated
Alkene polyalcohol, from from the viewpoint of the reactivity of polyisocyanates (a2), preferably using the polyoxygenated with 2~6 hydroxyls
Alkene polyalcohol, more preferably with 2~4 hydroxyls.
On the content of the alkylene oxide structure in above-mentioned polyurethane (A), obtained from by improving the hydrophily of polyurethane
From the viewpoint of more excellent stain resistance and whitening resistance, preferred 5~30mol/kg scope, more preferably 10~20mol/kg's
Scope, further preferred 13~17mol/kg scope.
As above-mentioned polyoxyalkylene polyol (a1), flexibility is assigned to adhesive, is obtained to the further of adherend
From the viewpoint of excellent wetability, polyoxypropylene diols and/or polyoxyethylene polyoxypropylene triol are preferably comprised, is more preferably contained
There are polyoxypropylene diols and polyoxyethylene polyoxypropylene triol.
In addition, as the oxygen ethylene unit in above-mentioned polyoxyalkylene polyol (a1) and the mol ratio [EO/ of oxypropylene structure
PO], from the viewpoint of it can further improve stain resistance and whitening resistance by improving the hydrophily of polyurethane, preferably
5/95~60/40 scope, more preferably 10/90~30/70 scope.
As the number-average molecular weight of the above-mentioned polyalcohol (a ' 1) containing above-mentioned polyoxyalkylene polyol (a1), from good
From the viewpoint of bonding physical property and the mechanical strength of bonding epithelium, preferably 500~6,000 scope, more preferably 800~3,000
Scope.It should be noted that the number-average molecular weight of above-mentioned polyalcohol (a ' 1) represents to exist by gel permeation chromatography (GPC) method
The value determined under the conditions of below.
Determine device：High speed GPC devices (TOSOH Co., Ltd's system " HLC-8220GPC ")
Post：Following posts of TOSOH Co., Ltd are connected in series use.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector：RI (differential refractometer)
Column temperature：40℃
Eluent：Tetrahydrofuran (THF)
Flow velocity：1.0mL/ minute
Injection rate：100 μ L (the mass % of sample solution concentration 0.4 tetrahydrofuran solution)
Standard specimen：Calibration curve is made using following polystyrene standards.
(polystyrene standard)
TOSOH Co., Ltd's system " TSKgel polystyrene standards A-500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards A-1000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards A-2500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards A-5000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-1 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-2 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-4 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-10 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-20 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-40 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-80 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-128 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-288 "
TOSOH Co., Ltd's system " TSKgel polystyrene standards F-550 "
In addition, above-mentioned polyalcohol (a ' 1) can also be as needed and with the chain extender of number-average molecular weight 50~400.
As above-mentioned chain extender, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-PD, 1,3- third can be used
Glycol, DPG, BDO, 1,3-BDO, 1,5-PD, 1,5- hexylene glycols, 1,6- hexylene glycols, 1,7- heptan two
Alcohol, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 3- methyl isophthalic acids are 5- pentanediols, 2- butyl -2- ethyl glycols, new
Pentanediol, Isosorbide-5-Nitrae-cyclohexane diol, 1,4-CHDM etc..These chain extenders can be used alone, can also and with 2 kinds
More than.
As above-mentioned polyisocyanates (a2), can use for example XDI, phenylene diisocyanate,
The aromatic polyisocyanates such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate；Hexa-methylene two
Isocyanates, lysine diisocyanate, cyclohexane diisocyanate, IPDI, 4,4 '-dicyclohexyl first
The aliphatic such as alkane diisocyanate, tetramethylxylylene diisocyanate or ester ring type polyisocyanates etc..These polyisocyanates
Cyanate can be used alone, and can also use two or more.Among these materials, from good bonding force is kept, one can be entered
Step suppress after when discoloration from the viewpoint of, preferably using aliphatic or ester ring type polyisocyanates.
As above-mentioned polyurethane (A) manufacture method, can enumerate for example with relative to possessed by polyisocyanates (a2)
The mol ratio of NCO, the mol ratio of hydroxyl possessed by polyalcohol (a ' 1), which turns into excessive mode, makes the two carry out instead
The method answered.It should be noted that above-mentioned reaction can also be carried out in organic solvent described later (D).In addition, polyalcohol (a '
1) it disposably can all feed intake, reaction can also be controlled to be fed intake while being divided into more than 2 times.As above-mentioned polyalcohol (a '
1) mol ratio (NCO/OH) of hydroxyl possessed by and NCO possessed by polyisocyanates (a2), controlled from reactivity
Easiness and bonding film mechanical strength from the viewpoint of, preferably 0.3~0.99 scope, more preferably 0.4~0.9 model
Enclose.
As above-mentioned polyurethane (A) weight average molecular weight, physical property is bonded and to adherend from that can take into account at a high level
From the viewpoint of wetability, preferably 50,000~300,000 scope, more preferably 70,000~200,000 scope.Need
It is noted that the weight average molecular weight of above-mentioned polyurethane (A) represents to survey in the same manner as the number-average molecular weight of above-mentioned polyalcohol (a ' 1)
Fixed value.
As above-mentioned crosslinking agent (B), such as polyisocyanate crosslinker, epoxy crosslinking agent, melamine can be used to hand over
Join agent etc..These crosslinking agents can be used alone, and can also use two or more.Among these materials, from polyurethane (A) institute
The hydroxyl reaction having, good bonding physical property, stain resistance and whitening resistance are obtained by the high crosslink density of adhesive
From the viewpoint of property, preferably using isocyanate crosslinking.
As above-mentioned polyisocyanate crosslinker, toluene di-isocyanate(TDI), chlorophenylene diisocyanates, six methylenes can be used
Group diisocyanate, tetramethylene diisocyanate, IPDI, methyl diphenylene diisocyanate, hydrogenation
The polyisocyanates such as methyl diphenylene diisocyanate, XDI；The three of hexamethylene diisocyanate
Hydroxymethyl-propane addition product, the trimethylolpropane addition product of toluene di-isocyanate(TDI), three hydroxyls of IPDI
Methylpropane addition product, the trimethylolpropane addition product of XDI, hexamethylene diisocyanate
Isocyanuric acid ester body (the ト bodies of ヌ レ mono-), the isocyanuric acid ester body of toluene di-isocyanate(TDI), the isocyanide of IPDI
The isocyanuric acid ester body etc. of urea acid esters body, XDI.These crosslinking agents can be used alone, can also be simultaneously
Use two or more.
As above-mentioned crosslinking agent (B) usage amount, from obtaining the sight of good bonding physical property, stain resistance and whitening resistance
Point sets out, relative to the scope of the mass parts of above-mentioned polyurethane (A) 100, preferably 0.01~20 mass parts, more preferably 0.1~
The scope of 15 mass parts.
Above-mentioned carbodiimide compound (C) be for showing excellent whitening resistance, and no matter base material, adherend such as
What and various adherends are shown with the required composition of excellent wetability and stain resistance.As sub- by using above-mentioned carbon two
Amines (C) and the reasons why obtain the effect above, can enumerate prevent it is high it is damp and hot it is lower caused by derive from the analyte of base material
It is transferred on adherend.
As above-mentioned carbodiimide compound (C), such as N, N '-dicyclohexylcarbodiimide, N can be used, N '-two is different
Propyl group carbodiimide, 1- ethyls -3- (3- dimethylaminopropyls) carbodiimide, N- [3- (dimethylamino) propyl group]-N '-second
Base carbodiimide, N- [3- (dimethylamino) propyl group]-N '-ethyl carbodiimide methiodide compound, the N- tert-butyl groups-N '-ethyl
Carbodiimide, N- cyclohexyl-N '-(2- morpholinoethyls) carbodiimide meso-p-methyl benzenesulfonic acid, N, N '-di-t-butyl carbon
The carbodiimide compound such as diimine, N, N '-di-p-tolyl carbodiimide；To be more in the presence of carbodiimidization catalyst
Isocyanates passes through poly- carbodiimide etc. obtained by known condensation reaction.These carbodiimide compounds can be used alone,
And two or more can also be used.Among these materials, preferably using with NCO carbodiimide compound, this be because
Reacted for the hydroxyl of itself and polyurethane (A), can obtain more excellent stain resistance and whitening resistance.
As above-mentioned carbodiimide compound (C), such as " Carbodilite V-02 ", " Carbodilite V-02-
L2”、“Carbodilite V-04”、“Carbodilite V-05”、“Carbodilite V-07”、“Carbodilite V-
09”、“Carbodilite E-01”“Carbodilite E-02”、“Carbodilite E-03A”、“Carbodilite E-
04 " (more than, Nisshinbo Chemical Co., Ltd system) etc. can be obtained in the form of commercially available product.
For above-mentioned carbodiimide compound (C) dosage, from obtaining excellent whitening resistance, the wetability to adherend
It is preferably the scope of 0.1~7 mass parts relative to the mass parts of above-mentioned polyurethane (A-1) 100 from the viewpoint of stain resistance,
The more preferably scope of 0.5~5 mass parts.
Above-mentioned organic solvent (D) is used for manufacture stability, the coating of adhesive composition for improving polyurethane (A-1),
The ester solvent such as ethyl acetate, methyl acetate, butyl acetate can be used；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.
Ketone solvent；The aliphatic hydrocarbon solvents such as heptane, hexane, hexamethylene, hexahydrotoluene；Toluene, ortho-xylene, meta-xylene, to two
The aromatic hydrocarbon solvents such as toluene；Alcoholic solvents such as methanol, ethanol, isopropanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol etc..These are organic molten
Agent can be used alone, and can also use two or more.
As above-mentioned organic solvent (D) usage amount, from the viewpoint of coating, relative to above-mentioned polyurethane (A) 100
Mass parts are preferably the scope of the scope of 20~200 mass parts, more preferably 40~100 mass parts.
As the adhesive composition of the present invention, contain above-mentioned polyurethane (A), above-mentioned crosslinking agent (B), above-mentioned carbodiimide
Compound (C) and organic solvent (D) are used as required composition, but from the wetability that can further improve to adherend, and
Being significantly increased for bonding force can also be suppressed under moisture-proof thermal environment, gone out in terms of further improving the stain resistance to adherend
Hair, preferably the hydroxyl also more than at least one containing polyoxyethylene glycol by monoacid be esterified obtained by carboxylate (E).
The reasons why as the effect above is obtained by using above-mentioned carboxylate (E), can enumerate can assign to adhesive
Further flexibility, the reasons why hydrophily is such.
As the number-average molecular weight of above-mentioned polyoxyethylene glycol, from obtaining binding agent based softness and bringing to quilt
The good wetability of viscous thing, and from the viewpoint of the binding agent based stain resistance oozed out can be improved, preferably 100
~1,500 scope, more preferably 150~1,000 scope.It should be noted that the number of above-mentioned polyoxyethylene glycol is divided equally
Son amount represent determined in the same manner as the number-average molecular weight of above-mentioned polyalcohol (a ' 1) obtained by value.
As above-mentioned monoacid, can use for example butyric acid, valeric acid, caproic acid, enanthic acid, 2 ethyl hexanoic acid, octanoic acid, n-nonanoic acid,
Capric acid, laurate, myristic acid, pentadecanoic acid, palmitic acid, Heptadecanoic acide, stearic acid, arachidic acid, behenic acid, lignoceric acid
Deng saturated fatty acid；Oleic acid, elaidic acid, linoleic acid, leukotrienes, arachidonic acid, eicosenoic acid, eicosapentaenoic acid, mustard
Unrighted acids such as acid, docosahexaenoic acid, castor oil acid etc..It is good with polyurethane from obtaining among these materials
Compatibility from the viewpoint of, preferably using carbon number 6~18 saturated fatty acid and/or carbon number 14~18 insatiable hunger
And aliphatic acid, more preferably use more than a kind of the monoacid in 2 ethyl hexanoic acid, laurate and oleic acid.
For above-mentioned carboxylate (E) dosage, from obtaining the excellent wetability to adherend and under moisture-proof thermal environment
The stain resistance to adherend from the viewpoint of, be preferably 1~50 mass parts relative to the mass parts of above-mentioned polyurethane (A) 100
Scope, more preferably 5~30 mass parts scope.
The adhesive composition of the present invention is used as required composition, further preferably above-mentioned (E) using above-mentioned (A)~(D) composition
Composition, it can also also contain other additives as needed.
As above-mentioned other additives, such as antioxidant, plasticizer, antirust agent, thixotropic agent, scattered can be used
Agent, sensitizer, urethanation catalyst, polymerization inhibitor, levelling agent, tackifier, surfactant etc..These additives can be independent
Use, and two or more can also be used.
As the manufacture method of the adhesive composition of the present invention, it can enumerate and for example be dissolved in above-mentioned organic solvent (D)
Above-mentioned polyurethane (A), above-mentioned crosslinking agent (B), above-mentioned carbodiimide compound (C) and upper are added in the mixture obtained by thus
State carboxylate (E) and the method mixed.
More than, adhesive composition of the invention can obtain whitening resistance under moisture-proof thermal environment and to adherend
The excellent bonding epithelium of stain resistance.In addition, in the case where making above-mentioned adhesive composition also contain specific carboxylate,
In addition to the above-described effects, additionally it is possible to further improve to the wetability of adherend and under moisture-proof thermal environment to being glued
The stain resistance of thing.Therefore, adhesive composition of the invention can be especially suitable for the adhesive layer of surface protection film.
As the method that surface protection film is manufactured using above-mentioned adhesive composition, can enumerate above-mentioned adhesive for example
Composition is coated on plastic basis material, is dried it, solidification, is thus obtained adhesive layer, glued next, mold release film is fitted in into this
Close the method on layer.
As above-mentioned plastic basis material, can use for example using polyethylene terephthalate, poly- naphthalenedicarboxylic acid second two
The polyester such as alcohol ester, polybutylene terephthalate (PBT), polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene
Piece or film obtained by vinyl alcohol, polyurethane, polyamide, polyimides etc..The surface of these plastic basis materials can implement to be stripped
Processing, antistatic process, sided corona treatment etc..In addition, the thickness of these above-mentioned plastic basis materials is, for example, 10~200 μm of scope.
As the method that above-mentioned adhesive composition is coated on to above-mentioned plastic basis material, it can enumerate and utilize roll coater, intaglio plate
The coating method of coating machine, trans coating machine, flush coater, Kohler coater, die coating machine etc..
Organic solvent (D) dried thickness of coated adhesive layer is, for example, 5~100 μm of scope.
, can as the method for drying the adhesive composition on above-mentioned plastic basis material after coating adhesive composition
Enumerating for example makes it in 50~120 DEG C of methods for drying 30 seconds~10 minutes.In addition, after drying, from the sight for promoting curing reaction
Point sets out, and for example can carry out aging in the range of 30 DEG C~50 DEG C.
Embodiment
Hereinafter, using embodiment, the present invention will be described in more detail.
[synthesis example 1]
<The synthesis of polyurethane (A-1)>
In with mixer, the reaction vessel for flowing back cooling tube, nitrogen ingress pipe, thermometer, by PEPA
(Kuraray Co., Ltd.s system " Kuraray Polyol P1010 ", number-average molecular weight：1,000th, hereinafter referred to as
“P1010”.) 330 mass parts, hexamethylene diisocyanate (it is following, be abbreviated as " HDI ".) 150 mass parts, tin dilaurate two
The mass parts of tin octylate 0.01, the mass parts of ethyl acetate 430 are added in detachable flask, are heated to 70 DEG C.Using based on two
After the titration of butylamine and hydrochloric acid confirms that NCO containing ratio reaches the containing ratio calculated by addition, 40 are cooled to
℃.Next, by polyoxyethylene polyoxypropylene triol, (Sanyo Chemical Industries Co., Ltd.'s system " SUNNIX GL-3000 ", counts equal molecule
Amount；3,000, mol ratio [EO/PO]=25/75, hereinafter referred to as " GL-3000 ".) 960 mass parts, tin dilaurate dioctyl tin
0.02 mass parts, the mass parts of ethyl acetate 345 are added in detachable flask, are reacted 3 hours, are thus obtained non-volatile at 70 DEG C
Composition：65 mass %, viscosity：10,000mPas, weight average molecular weight：130,000th, the content of polyoxyalkylene：12mol/kg's
Polyurethane (A-1).
[synthesis example 2]
<The synthesis of polyurethane (A-2)>
In with mixer, the reaction vessel for flowing back cooling tube, nitrogen ingress pipe, thermometer, by polyoxypropylene diols (number
Average molecular weight：1,000, hereinafter referred to as " PPG1000 ".) 330 mass parts, the mass parts of HDI 150, tin dilaurate dioctyl tin
0.2 mass parts, the mass parts of ethyl acetate 430 are added in detachable flask, are heated to 70 DEG C.Using based on dibutylamine and salt
After the titration of acid confirms that NCO containing ratio reaches the containing ratio calculated by addition, 40 DEG C are cooled to.Next,
Will the mass parts of GL-3000 960, the mass parts of ethyl acetate 345 add detachable flask in, 70 DEG C react 3 hours, thus
Obtain nonvolatile component：65 mass %, viscosity：15,500mPas, weight average molecular weight：130,000th, the content of polyoxyalkylene：
16mol/kg polyurethane (A-2).
[synthesis example 3]
<The synthesis of polyurethane (A-3)>
In with mixer, the reaction vessel for flowing back cooling tube, nitrogen ingress pipe, thermometer, by polyoxyethylene polyoxy third
Alkene triol (Japan Oil Co's system " Uniluve 50TG-32 ", number-average molecular weight：2,800, mol ratio [EO/PO]=57/43,
Hereinafter referred to as " 50TG-32 ".) 1,800 mass parts, the mass parts of HDI 150, the mass parts of tin dilaurate dioctyl tin 0.2, acetic acid
The mass parts of ethyl ester 830 are added in detachable flask, are heated to 70 DEG C, are made its reaction, thus obtain nonvolatile component：75 matter
Measure %, viscosity：2,000mPas, weight average molecular weight：70,000th, the content of polyoxyalkylene：18mol/kg polyurethane (A-3).
[embodiment 1]
Relative to the mass parts of nonvolatile component 100 of the polyurethane (A-1) obtained in synthesis example 1, coordinate Nisshinbo strain
Formula commercial firm carbodiimide compound " Carbodilite V-05 " (it is following, it is abbreviated as " V-05 ".) 1 mass parts, as crosslinking
The hexamethylene diisocyanate of agent isocyanuric acid ester body (Asahi Kasei Corporation's system " and Duranate TKA-100 ", below
It is abbreviated as " TKA-100 ".) 10 mass parts, obtain adhesive composition.
Then, on the surface of the polyethylene terephthalate film of 50 μm of thickness with dried thickness as 10 μm
Mode is coated with above-mentioned adhesive composition, is dried 3 minutes at 80 DEG C.To the poly- of thickness 38 μm of its coating surface through demoulding processing
Ethylene glycol terephthalate film, conserved 3 days at 40 DEG C, thus obtain surface protection film.
[embodiment 2~10]
Change the species of polyurethane (A) used, crosslinking agent (B) and carbodiimide compound (C) as shown in table 1
And/or amount, in addition, operate similarly to Example 1, obtain adhesive composition and surface protection film.
[comparative example 1]
In addition to without using carbodiimide compound (C), operate similarly to Example 1, obtain adhesive composition
And surface protection film.
[comparative example 2~4]
Change the species and/or amount of polyurethane (A) used and crosslinking agent (B) as shown in table 2, in addition, with than
Similarly operated compared with example 1, obtain adhesive composition and surface protection film.
[assay method of bonding force]
Using the surface protection film obtained in embodiment and comparative example cut into wide 20mm surface protection film and as examination
Test piece.Mold release film is peeled off from test film, for glass plate, with 2kg rollers reciprocal 2 in a manner of bond area turns into 20mm × 60mm
It is secondary to be pasted.180 degree peel strength is carried out after pasting 24 hours in the environment of 23 DEG C, humidity 50%, is set to initial adhesion
Power (N/25mm).In addition, after above-mentioned stickup, placed 72 hours under conditions of 85 DEG C, humidity 85%, then under 23 DEG C of environment
After placing 24 hours, 180 degree peel strength is carried out, is set to bonding force (N/25mm) after wet-heat resisting.
[evaluation method of whitening resistance]
The mold release film of the surface protection film obtained in embodiment and comparative example is peeled off, is pasted on glass plate.For this
The mist degree (%) of test body, using nephelometer " NDH5000 " (the electric color of Japan industrial (strain) system) and according to JISK7361-1-1997
It is measured.After then, the test film of gained is placed 100 hours under conditions of 85 DEG C, 85%RH (it is following, it is abbreviated as " resistance to
After damp heat test ".), taken out in the environment of 23 DEG C, 50%RH.After taking-up, nephelometer was utilized within 10 minutes
" NDH5000 " (the electric color of Japan industrial (strain) system) is simultaneously measured according to JISK7361-1-1997 to mist degree (%), according to following
Mode evaluates whitening resistance.
“○”：The difference of mist degree (%) value before and after hot resistance test is less than 0.3%.
“Δ”：The difference of mist degree (%) value before and after hot resistance test is 0.3% less than 1%.
“×”：The difference of mist degree (%) value before and after hot resistance test is more than 1%.
[evaluation method of stain resistance]
The mold release film of the surface protection film obtained in embodiment and comparative example is peeled off, is pasted on glass plate.Now, exist
Bubble is introduced between bonding film and glass plate.The test body is placed 72 hours under conditions of 85 DEG C, humidity 85%.Then
After being placed 24 hours under 23 DEG C of environment, bonding film is peeled off from glass plate with hand, from the irradiated LED of glass plate, mesh
Evaluated depending on observation pollution situation and as shown below.
“○”；Glass plate does not pollute completely.
“△”；Only pollution is confirmed in a part for glass plate.
“×”；Pollution is confirmed in the whole surface of glass plate.
[table 1]
[table 2]
Abbreviation in table 1~2 is illustrated.
“V-07”；Nisshinbo Co. Ltd. system carbodiimide compound " Carbodilite V-07 "
“V-09”；Nisshinbo Co. Ltd. system carbodiimide compound " Carbodilite V-09 "
“P301-75E”；Trimethylolpropane addition product (the Asahi Chemical Corp of hexamethylene diisocyanate
System " Duranate P301-75E ")
[embodiment 11]
10 mass parts polyoxyethylene glycols (the equal molecule of number is further added in the adhesive composition of the gained of embodiment 1
Amount；200) two ends by 2 ethyl hexanoic acid be esterified obtained by carboxylate (E-1) be used as carboxylate (E), obtain adhesive group
Compound.
Next, turn into 10 μm on the surface of the polyethylene terephthalate film of 50 μm of thickness with dried thickness
Mode be coated with above-mentioned adhesive composition, 80 DEG C dry 3 minutes.To the poly- of thickness 38 μm of its coating surface through demoulding processing
Ethylene glycol terephthalate film, conserved 3 days at 40 DEG C, thus obtain surface protection film.
[embodiment 12~18]
Change polyurethane (A), crosslinking agent (B), carbodiimide compound (C) and carboxylate (E) used as shown in table 3
Species and/or amount, in addition, operate similarly to Example 1, obtain adhesive composition and surface protection film.
[comparative example 6]
In addition to without using carbodiimide compound (C), operate similarly to Example 1, obtain adhesive composition
And surface protection film.
[comparative example 5~8]
Change the species and/or amount of polyurethane (A) used and crosslinking agent (B) as shown in table 4, in addition, with than
Similarly operated compared with example 5, obtain adhesive composition and surface protection film.
[evaluation method of wetability]
The surface protection film obtained in embodiment and comparative example is cut into wide 5cm, long 15cm rectangle and stripping
Mold release film, will thus obtained by surface protection film as test film.The both ends of the test film are held with hand, makes its bending, makes
The central part of the adhesive layer exposed decontrols hand after being adhered to glass plate, and measure is until bonding film is pasted on glass plate by deadweight
Number of seconds.
[table 3]
[table 4]
Abbreviation in table 3~4 is illustrated.
“E-2”：Polyoxyethylene glycol (number-average molecular weight：600) two ends by 2 ethyl hexanoic acid be esterified obtained by esterification
Thing
“E-3”；Polyoxyethylene glycol (number-average molecular weight：500) a end by laurate be esterified obtained by carboxylate
Understand：Under moisture-proof thermal environment, the whitening resistance of adhesive composition of the invention and to the resistance to of adherend
Contaminative is also excellent.In addition, understand：It is excellent to the wetability of adherend for the embodiment 9~16 containing carboxylate (E)
It is different, additionally it is possible to suppress the rise of the bonding force after hot resistance test.
On the other hand, comparative example 1~8 is the embodiment that carbodiimide compound (C) is not used, and confirms adherend
Pollution.
Claims (10)
1. a kind of adhesive composition, it is characterised in that contain：Polyurethane (A), crosslinking agent (B) with more than 2 hydroxyls,
Carbodiimide compound (C) and organic solvent (D).
2. adhesive composition according to claim 1, wherein, the polyurethane (A) has more from polyoxyalkylene
First alcohol (a1) and the structure of polyisocyanates (a2).
3. adhesive composition according to claim 2, wherein, the polyoxyalkylene polyol (a1) contains polyoxypropylene
Glycol and/or polyoxyethylene polyoxypropylene triol.
4. adhesive composition according to claim 3, wherein, the polyoxyalkylene polyol (a1) contains polyoxypropylene
Glycol and polyoxyethylene polyoxypropylene triol, oxygen ethylene unit and mole of oxypropylene structure in polyoxyalkylene polyol (a1)
Than the scope that 5/95~60/40 is expressed as with EO/PO.
5. adhesive composition according to claim 2, wherein, the content of the alkylene oxide structure in the polyurethane (A)
For 5~30mol/kg scope.
6. adhesive composition according to claim 1, wherein, the usage amount of the carbodiimide compound (C) is relative
In the scope that the mass parts of the polyurethane (A) 100 are 0.1~7 mass parts.
7. adhesive composition according to claim 1, wherein, the crosslinking agent (B) is polyisocyanate crosslinker.
8. adhesive composition according to claim 1, its hydroxyl also more than at least one containing polyoxyethylene glycol
By monoacid be esterified obtained by carboxylate (E).
9. adhesive composition according to claim 8, wherein, the usage amount of the carboxylate (E) is relative to polyurethane
(A) 100 mass parts are the scope of 1~50 mass parts.
10. a kind of surface protection film, it has the curing overlay film of adhesive composition according to any one of claims 1 to 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-141365 | 2015-07-15 | ||
| JP2015141365 | 2015-07-15 | ||
| PCT/JP2016/064144 WO2017010158A1 (en) | 2015-07-15 | 2016-05-12 | Pressure-sensitive adhesive composition and surface protection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107835845A true CN107835845A (en) | 2018-03-23 |
| CN107835845B CN107835845B (en) | 2021-06-25 |
Family
ID=57756942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680041066.2A Active CN107835845B (en) | 2015-07-15 | 2016-05-12 | Adhesive composition and surface protective film |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN107835845B (en) |
| TW (1) | TWI677549B (en) |
| WO (1) | WO2017010158A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796921A (en) * | 2019-01-30 | 2019-05-24 | 广东盈通新材料有限公司 | A kind of modified polyurethane adhesive, composite water-proof joint strip including modified polyurethane adhesive and its preparation method and application |
| CN111100585A (en) * | 2018-10-29 | 2020-05-05 | 琳得科株式会社 | Anti-scattering adhesive sheet |
| CN112236494A (en) * | 2018-08-01 | 2021-01-15 | Dic株式会社 | Adhesive composition and surface protective film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020095484A1 (en) * | 2018-11-06 | 2020-05-14 | Dic株式会社 | Adhesive composition and surface protective film |
| JP6863538B2 (en) * | 2018-11-29 | 2021-04-21 | Dic株式会社 | Adhesive composition and surface protective film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155321A (en) * | 2001-09-10 | 2003-05-27 | Toyo Ink Mfg Co Ltd | Urethane resin composition |
| JP2003292928A (en) * | 2002-02-04 | 2003-10-15 | Toyo Ink Mfg Co Ltd | Urethane resin adhesive and laminate |
| JP2006182795A (en) * | 2004-12-24 | 2006-07-13 | Mitsubishi Chemicals Corp | Polyurethane pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet and surface-protecting film |
| JP2007277484A (en) * | 2006-04-11 | 2007-10-25 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and surface-protective film |
| CN103068873A (en) * | 2010-08-06 | 2013-04-24 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for producing surface layer of leather-like sheet, laminate and leather-like sheet |
| CN104004464A (en) * | 2013-02-22 | 2014-08-27 | 日东电工株式会社 | Surface protective film |
| US8906976B2 (en) * | 2011-11-01 | 2014-12-09 | Hyundai Motor Company | Polyurethane compositions for an automotive seat |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5456440B2 (en) * | 2009-01-30 | 2014-03-26 | 日東電工株式会社 | Dicing tape integrated wafer back surface protection film |
| KR101404875B1 (en) * | 2009-12-04 | 2014-06-09 | 도요보 가부시키가이샤 | Highly adhesive thermoplastic resin film |
| JP6092034B2 (en) * | 2013-07-30 | 2017-03-08 | 日東電工株式会社 | Surface protective film and optical member |
-
2016
- 2016-05-12 WO PCT/JP2016/064144 patent/WO2017010158A1/en active Application Filing
- 2016-05-12 CN CN201680041066.2A patent/CN107835845B/en active Active
- 2016-05-25 TW TW105116183A patent/TWI677549B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155321A (en) * | 2001-09-10 | 2003-05-27 | Toyo Ink Mfg Co Ltd | Urethane resin composition |
| JP2003292928A (en) * | 2002-02-04 | 2003-10-15 | Toyo Ink Mfg Co Ltd | Urethane resin adhesive and laminate |
| JP2006182795A (en) * | 2004-12-24 | 2006-07-13 | Mitsubishi Chemicals Corp | Polyurethane pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet and surface-protecting film |
| JP2007277484A (en) * | 2006-04-11 | 2007-10-25 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and surface-protective film |
| CN103068873A (en) * | 2010-08-06 | 2013-04-24 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for producing surface layer of leather-like sheet, laminate and leather-like sheet |
| US8906976B2 (en) * | 2011-11-01 | 2014-12-09 | Hyundai Motor Company | Polyurethane compositions for an automotive seat |
| CN104004464A (en) * | 2013-02-22 | 2014-08-27 | 日东电工株式会社 | Surface protective film |
Non-Patent Citations (3)
| Title |
|---|
| 中国化纤总公司: "《化学纤维及原料实用手册》", 30 June 1996, 中国纺织出版社 * |
| 汪多仁: "《现代高分子材料生产及应用手册》", 31 May 2002, 中国石化出版社 * |
| 沈春林 等: "《建筑涂料手册》", 31 March 2002, 中国建筑工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112236494A (en) * | 2018-08-01 | 2021-01-15 | Dic株式会社 | Adhesive composition and surface protective film |
| CN112236494B (en) * | 2018-08-01 | 2022-07-26 | Dic株式会社 | Adhesive composition and surface protective film |
| CN111100585A (en) * | 2018-10-29 | 2020-05-05 | 琳得科株式会社 | Anti-scattering adhesive sheet |
| CN109796921A (en) * | 2019-01-30 | 2019-05-24 | 广东盈通新材料有限公司 | A kind of modified polyurethane adhesive, composite water-proof joint strip including modified polyurethane adhesive and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017010158A1 (en) | 2017-01-19 |
| TWI677549B (en) | 2019-11-21 |
| CN107835845B (en) | 2021-06-25 |
| TW201708483A (en) | 2017-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107835845A (en) | Adhesive composition and surface protection film | |
| JP6070633B2 (en) | Re-peelable urethane pressure-sensitive adhesive composition, re-peelable pressure-sensitive adhesive film obtained using the same, and film for protecting the surface of optical parts | |
| JP6014926B2 (en) | Adhesive and adhesive tape | |
| TWI570145B (en) | Moisture-curable polyurethane hot-melt resin composition, adhesive, and article | |
| TWI595063B (en) | Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive | |
| JP6582513B2 (en) | Urethane prepolymer and two-component urethane adhesive using the same | |
| TW201022392A (en) | Adhesive laminate | |
| JP6447083B2 (en) | Moisture curable polyurethane hot melt resin composition, adhesive and laminate | |
| JP6494264B2 (en) | Surface protection adhesive sheet | |
| JP2018508615A (en) | Chemical resistant polyurethane adhesive | |
| KR20160142284A (en) | Polyester adhesive composition and adhesive sheet | |
| TW201012888A (en) | Adhesive material, pressure-sensitive adhesive sheet, and use thereof | |
| CN108300366B (en) | Adhesive sheet | |
| KR20130070568A (en) | Adhesive laminate and surface protective sheet | |
| JP6519687B1 (en) | Pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing hydroxyl terminated urethane prepolymer | |
| JP5835525B1 (en) | Adhesive composition and adhesive film | |
| JP6032388B1 (en) | Adhesive composition and surface protective film | |
| WO2021132558A1 (en) | Two-part curable urethane adhesive, cured product of two-part curable urethane adhesive, and urethane adhesive sheet | |
| JP6350764B2 (en) | Polyurethane composition and sheet | |
| JP6763365B2 (en) | Adhesive sheet | |
| WO2019240046A1 (en) | Two-component urethane-based adhesive composition | |
| KR102405505B1 (en) | Moisture-curable polyurethane hot-melt resin composition, and articles using the same | |
| JP2024024542A (en) | Urethane prepolymer and its manufacturing method | |
| JP2010111861A (en) | Heat-resistant self-adhesive laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |