CN109796841A - Thermohardening type removes coating agent and stripping film - Google Patents
Thermohardening type removes coating agent and stripping film Download PDFInfo
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- CN109796841A CN109796841A CN201811342829.4A CN201811342829A CN109796841A CN 109796841 A CN109796841 A CN 109796841A CN 201811342829 A CN201811342829 A CN 201811342829A CN 109796841 A CN109796841 A CN 109796841A
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Abstract
The present invention provides be capable of forming excellent appearance of film and the novel thermosetting type of the cured film of stripping performance and excellent solvent resistance removing coating agent.The thermohardening type removing coating agent for self condensing object (B) and acid catalyst (C) of [technological means] containing melamine resin (A), the aliphatic hydroxyl carboxylic acid (b) of carbon atom number 12-24.
Description
Technical field
The present invention relates to thermohardening type removing coating agents (removing コ ー テ ィ Application グ drug) and stripping film (removing Off ィ Le system).
Background technique
Using polyethylene terephthalate film as the transparency of the biaxially oriented polyester film of representative, dimensional stability, machine
Tool characteristic, chemical-resistant etc. are had excellent performance, and have been used in various industrial circles.In recent years, it has been widely used for various
Optical film, and the basement membranes such as prismatic lens, light diffusing sheet, reflecting plate, touch panel for being used for LCD component and antireflection basement membrane
Etc. various uses.In addition, the case where basement membrane as stripping film uses is also more, for manufacturing bonding sheet, adhesive tape, touch
Panel protective film, ceramic green sheet and be widely used in electronic material purposes.
Previous stripping film is mainly formd in polyester film surface by the silicone resin class remover with fissility
Resin coating film formed peeling layer stripping film.However, when forming the resin coating film using silicone remover, it is indicated that due to
Low molecular weight silicone compounds from silicone remover are transferred to the adhesive layer surface of bonding sheet from the resin coating film, deposit
A possibility that breaking down a possibility that the bonding force of adhesive phase reduces and through the electronic component of the adhering adhesive sheet.
In addition, the manufacturing process of capacitor ceramic green sheet and printed base plate, various electronic components sealing process etc. used in
In stripping film, similarly point out to generate undesirable condition because above-mentioned silicone compounds are shifted to electronic component surface.
In order to inhibit the pollution as caused by above-mentioned silicone compounds, it is proposed that non-silicone remover is (referring to patent document 1
With patent document 2).It is disclosed in patent document 1 and patent document 2 containing making polyvinyl alcohol or ethylene-vinyl alcohol copolymer
The non-silicone of chain alkyl side chain type (ペ Application ダ Application ト type) polymer made of reacting with chain alkyl isocyanates is removed
Agent.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2000-119608 bulletin
Patent document 2: Japanese Unexamined Patent Publication 5-295332 bulletin
Summary of the invention
Technical problems to be solved by the inivention
However, for above patent document 1 and remover disclosed in Patent Document 2, although the film formed by it
Stripping performance it is good, but since the film is not crosslinked, there are the low such technical problems of solvent resistance.In addition, by
It is low in dissolubility of the above-mentioned remover to various solvents, therefore gonorrhoea or bumps etc. are easy to appear by the film that the remover is formed
Apparent unfavorable condition, there is also the technical problems that appearance of film difference is such.
The purpose of the present invention is to provide be capable of forming excellent appearance of film and stripping performance and excellent solvent resistance are consolidated
The novel thermosetting type for changing film removes coating agent.
Solve the technological means of technical problem
The present inventor further investigation as a result, it has been found that, by defined aliphatic hydroxyl carboxylic acid self condense object (fat
Oneself sour condensation product of race ヒ De ロ キ シ カ Le ボ Application) and defined melamine resin in be combined with the combination of acid catalyst
Object is able to solve above-mentioned technical problem, so as to complete the present invention.That is, the present invention relates to following thermohardening types to remove coating agent
And stripping film.
1. thermohardening type removes coating agent, the thermohardening type removing coating agent contains melamine resin (A), carbon atom
The aliphatic hydroxyl carboxylic acid (b) of number 12-24 self condenses object (B) and acid catalyst (C).
2. the thermohardening type as described in above-mentioned item 1 removes coating agent, wherein (A) ingredient contains from methylation melamine
The structural unit of amine and/or butylated melamines.
3. the thermohardening type as described in above-mentioned item 1 or 2 removes coating agent, wherein (B) ingredient is the fat of carbon atom number 18
Race's hydroxycarboxylic acid self condenses object.
4. the thermohardening type as described in any one of above-mentioned item 1-3 removes coating agent, wherein coated relative to the removing
The 100 weight % of total solid content of agent, the content of (B) ingredient are 1-50 weight %.
5. the thermohardening type as described in any one of above-mentioned item 1-4 removes coating agent, wherein (C) ingredient is organic sulfonic acid
And/or organic phosphoric acid.
6. the thermohardening type as described in any one of above-mentioned item 1-5 removes coating agent, wherein coated relative to the removing
The 100 weight % of total solid content of agent, the content of (C) ingredient are 1-10 weight %.
7. the thermohardening type as described in any one of above-mentioned item 1-6 removes coating agent, wherein the thermohardening type removing applies
It covers agent and also contains polyalcohol (D).
8. the thermohardening type as described in above-mentioned item 7 removes coating agent, wherein the weight ratio of (A) ingredient and (D) ingredient
[(A)/(D)] is 90/10-30/70.
9. cured film and plastics comprising being formed as the thermohardening type removing coating agent as described in any one of above-mentioned item 1-8
The stripping film of film.
10. the stripping film as described in above-mentioned item 9, wherein the plastic foil is polyethylene terephthalate film.
Beneficial effect
Thermohardening type removing coating agent of the invention can form that peeling force is light, solvent resistance by the heated drying of short time
Excellent cured film (rapidly-curable).In addition, being transparent smooth cured film by the cured film that the coating agent is formed, and film
Excellent appearance.Further, which is suitable as the remover for the stripping film that base material film is polyester film.
Specific embodiment
Thermohardening type removing coating agent (hereinafter referred to as coating agent) of the invention is (following containing melamine resin (A)
Referred to as (A) ingredient), the aliphatic hydroxyl carboxylic acid (b) of carbon atom number 12-24 self condense object (B) (hereinafter referred to as (B) ingredient) and
The composition of acid catalyst (C) (hereinafter referred to as (C) ingredient).
(A) as long as ingredient melamine resin, then can not use various well known substances particularly restrictedly.Example
Such as, the resin containing the structural unit for carrying out the compound that free the following general formula (1) indicates can be enumerated.(A) ingredient is average poly-
It is right not particularly restricted, usually 1.1-10 or so.
[changing 1]
In formula (1), R1-R6It can be the same or different from each other, respectively indicate selected from hydrogen atom, methylol (- CH2OH), first
Oxygroup methyl (- CH2OCH3), ethoxyl methyl (- CH2OCH2CH3), n-butoxy methyl (- CH2OCH2CH2CH2CH3) and isobutyl
Oxygroup methyl (- CH2OCH(CH3)CH2CH3) in group.
From the viewpoint of balancing good from the rapidly-curable of coating agent and with the intermiscibility of following (B) ingredients, (A) at
Divide resin preferably containing the structural unit from methylated melamine and/or butylated melamines.Respectively, methyl
Change the substituent R that melamine refers to above-mentioned general formula (1)1-R6At least one of be methoxy (- CH2OCH3) object
Matter；Butylated melamines refer to that at least one of described substituent group is positive butoxymethyl (- CH2OCH2CH2CH2CH3), it is different
Butoxymethyl (- CH2OCH(CH3)CH2CH3) any one of substance.
From the viewpoint of having excellent fast curing, (A) ingredient preferably contains from above-mentioned R1-R6All methoxyl groups
Resin (the hereinafter referred to as full ether type methyl of the structural unit of full ether type (Off ル エ ー テ Le type) methylated melamine of methyl
Change melamine resin)；From with from the viewpoint of the intermiscibility of following (B) ingredients, preferably contains and come from the R1-R6All
Be positive any one of butoxymethyl, isobutoxymethyl full ether type butylated melamines structural unit resin
(hereinafter referred to as full ether type butylated melamine resins).In addition, from rapidly-curable and with the intermiscibility of following (B) ingredients
From the viewpoint of balancing good, preferably containing from the R1-R6At least one of for methoxy and remaining be respectively
The tree of the structural unit of the full ether type methylation butylated melamines of any one of n-butoxy methyl, isobutoxymethyl
Rouge (hereinafter referred to as full ether type methylation butylated melamine resins).
(A) ingredient can be commercially available product, such as can enumerate: サ イ メ Le 300, サ イ メ Le 301, サ イ メ Le 303LF,
サイメル350、サイメル370N、サイメル771、サイメル325、サイメル327、サイメル703、サイ
メル712、サイメル701、サイメル266、サイメル267、サイメル285、サイメル232、サイメル
235、サイメル236、サイメル238、サイメル272、サイメル212、サイメル253、サイメル254、
サ イ メ Le 202, サ イ メ Le 207, マ イ コ ー ト 506 (being manufactured above by オ Le ネ Network ス ジ ャ パ Application (strain))；ニカラ
ックMW-30M、ニカラックMW-30、ニカラックMW-30HM、ニカラックMW-390、ニカラックMW-100LM、
ニカラックMX-750LM、ニカラックMW-22、ニカラックMS-21、ニカラックMS-11、ニカラックMW-
24X、ニカラックMS-001、ニカラックMX-002、ニカラックMX-730、ニカラックMX-750、ニカラック
MX-708、ニカラックMX-706、ニカラックMX-042、ニカラックMX-035、ニカラックMX-45、ニカラッ
Network MX-43, ニ カ ラ ッ Network MX-417, ニ カ ラ ッ Network MX-410 (being manufactured above by (strain) three and chemistry)；ユーバン20SB,
ユーバン20SE60、ユーバン21R、ユーバン22R、ユーバン122、ユーバン125、ユーバン220、ユ
225, ユ ー バ Application of ー バ Application, 228, ユ ー バ Application 2020 (being manufactured above by Mitsui Chemicals (strain))；アミディアJ-820-60,
アミディアL-109-65、アミディアL-117-60、アミディアL-127-60、アミディア13-548、アミディアG-
821-60, ア ミ デ ィ ア L-110-60, ア ミ デ ィ ア L-125-60, ア ミ デ ィ ア L-166-60B (being manufactured above by DIC (strain))
Deng these can be used alone or are used in combination of two or more.(A) content of ingredient is not particularly restricted, from obtaining cured film
Solvent resistance from the viewpoint of, relative to total solid content 100 weight %, preferably 25-98 weight % or so of coating agent,
More preferably 30-95 weight % or so.In addition, " total solid content " refers to the complete of the coating agent other than following (E) ingredients
Portion's ingredient.It is same as below.
(B) ingredient is to confer to the ingredient of fissility, as long as the aliphatic hydroxyl carboxylic acid (b) of carbon atom number 12-24 is (following
Referred to as (b) ingredient) self condense object, then it is not particularly restricted.By making the object that self condenses of (B) ingredient (b) ingredient, coat
Agent can form transparent smooth cured film, and appearance of film is excellent.Although details are unknown, it is presumably due to (b) ingredient
The crystallinity of single compound is high, therefore in the film containing the single compound, forms film caused by being precipitated because of crystallization
Bumps caused by gonorrhoea and the insoluble component because being generated in film in film coated surface.On the other hand, thus it is speculated that due to (b) ingredient
The crystallinity for self condensing object it is low, therefore have no above-mentioned unfavorable condition in containing the film for self condensing object.
As long as (b) the aliphatic hydroxyl carboxylic acid of ingredient carbon atom number 12-24, then can not use particularly restrictedly
Various well known substances.For the carbon atom number of (b) ingredient, from the viewpoint of the light separation of cured film, carbon atom number
It is more preferably；But from the viewpoint of the light separation and excellent appearance of film that can have both cured film, (b) carbon of ingredient is former
Subnumber is usually 12-24 or so, preferably 14-22 or so, more preferably 16-20 or so；From the viewpoint of same, carbon atom
Number particularly preferably 18 or so.(b) ingredient is if it is the aliphatic hydroxyl carboxylic acid below of carbon atom number 11, the then removing of cured film
Property reduce；If it is the aliphatic hydroxyl carboxylic acid of 25 or more carbon atom number, then appearance of film deteriorates.In addition, the rouge in the present invention
Fat race hydroxycarboxylic acid refers to that intramolecular has the aliphatic monocarboxylic acid of a hydroxyl.
It as the specific example of (b) ingredient, such as can enumerate: the hydroxyls moon such as 2- hydroxylauric acid, 3- hydroxylauric acid
Cinnamic acid；The hydroxymyristic acids such as 2- hydroxymyristic acid, 3- hydroxymyristic acid；2- hydroxypentadecanoic acid, 3- hydroxypentadecanoic
The hydroxypentadecanoic acids such as acid；The hydroxy-palmitic acids such as 2- hydroxy-palmitic acid, 3- hydroxy-palmitic acid；2-hydroxystearic acid, 3- hydroxyl are hard
The hydroxy stearic acids such as resin acid, 12- hydroxy stearic acid；The hydroxyeicosanoic acids such as 2- hydroxyeicosanoic acid, 3- hydroxyeicosanoic acid；2-
The hydroxyls behenic acids such as hydroxyl behenic acid, 3- hydroxyl behenic acid；2- hydroxyl tetracosane acid, 3- hydroxyl 24
The hydroxyl tetracosane acids such as alkanoic acid；Ricinoleic acid；(principal component is hydrogenated castor oil fatty (hardening ヒ マ シ fatty acid oil)
12- hydroxy stearic acid)；And Castor Oil Fatty Acid (principal component is ricinoleic acid) etc..Wherein, from can have both light separation and
From the viewpoint of excellent appearance of film, preferably 2-hydroxystearic acid, 3- hydroxy stearic acid, 12- hydroxy stearic acid, castor oil
The aliphatic hydroxyl carboxylic acid of the carbon atom numbers 18 such as acid, hydrogenated castor oil fatty and Castor Oil Fatty Acid；From the easiness obtained
From the point of view of, more preferably 12- hydroxy stearic acid, ricinoleic acid.12- hydroxy stearic acid be industrially by rilanit special into
Row is hydrolyzed and is manufactured, or is obtained by hydrogenating to ricinoleic acid.Ricinoleic acid is obtained by being saponified castor oil
's.In addition, contain a small amount of stearic acid and palmitinic acid as impurity in the 12- hydroxy stearic acid obtained by above-mentioned hydrolysis, but
These also may be embodied in coating agent of the invention.
(B) ingredient is as obtained from self condensing (b) ingredient with various well known methods.This method is not by special
It limits, for example, (b) ingredient can be heated to 150-250 DEG C of temperature or so under non-active gas atmosphere, in toluene, diformazan
Pass through azeotropic in the presence of benzene by water in addition to going to system, while making its dehydrating condensation and obtaining.In addition it is also possible to which there are titanium classes
The catalyst such as compound, p-methyl benzenesulfonic acid, sulfuric acid.The example of commercially available product as (B) ingredient, can enumerate: PHF-33, PCF-30
(being manufactured above by her rattan liquefaction (strain))；K-PON306, K-PON402, K-PON404, K-PON406 (synthesize work by small storehouse above
Industry (strain) manufacture)；HSC-32, HSC-47, HSC-60D, HSC-95 (are manufactured by rich state's liquefaction (strain)) above；KF-3400,KF-
4500, KF-4013, KF-4055E, KF-40E (being manufactured above by ケ イ エ Off ト レ ー デ ィ Application グ (strain)) etc..
(B) hydroxyl value when hydroxyl value mentioned below (JIS K0070, identical) of ingredient is not particularly restricted, from light separation
From the viewpoint of, preferably 10-50mgKOH/g；From the viewpoint of same, more preferably 20-40mgKOH/g.In addition, (B)
Number-average molecular weight (the polystyrene scaled value obtained using gel permeation chromatography, when number-average molecular weight mentioned below of ingredient
It is identical) it is also not particularly restricted, from the viewpoint of the light separation and excellent appearance of film that can have both cured film, preferably
For 500-3,000 or so, more preferably 1,000-2,000 or so.Further, from can have both cured film light separation and
From the viewpoint of excellent appearance of film, (B) ingredient is preferably the 2-10 aggressiveness of (b) ingredient, more preferably 4-8 aggressiveness.
(B) ingredient is the structure that a hydroxyl and a carboxyl are respectively provided in a molecule, which can also be by
Esterification.There is a hydroxyl in a molecule by making (B) ingredient, coating agent of the invention is capable of forming that peeling force is light to be consolidated
Change film.Show an example of (B) constituent structure.
[changing 2]
(B) content of ingredient is not particularly restricted, from the sight for the solvent resistance that can have both light separation and cured film
From the point of view of point, relative to the 100 weight % of total solid content of coating agent, preferably 1-50 weight % or so, more preferably 2-30 weight
Measure % or so.
(C) as long as ingredient acid catalyst, then can not use various well known substances particularly restrictedly.It is specific and
Speech, such as can enumerate: the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid；And organic acid.As the organic acid, such as
It can enumerate: the carboxylic acids such as oxalic acid, acetic acid, formic acid；Methanesulfonic acid, trifluoromethanesulfonic acid, isoprene sulfonic acid, camphorsulfonic acid, hexane sulphur
Acid, perfluoroetane sulfonic acid, nonane sulfonic acid, decane sulfonic acid, hexadecane sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, isopropyl sulfonic acid, dodecane
The organic sulfonic acids such as base benzene sulfonic acid, naphthalene sulfonic acids, nonyl naphthalene sulfonic acids；Methyl phosphate ester acid, ethyl acid phosphate, propyl acid phosphorus
Acid esters, isopropyl acid phosphate, butyl phosphate ester acid, butoxyethyl group phosphate ester acid, octyl phosphate ester acid, 2- second
Base hexyl phosphate ester acid, decyl phosphate ester acid, lauryl phosphate ester acid, stearyl phosphate ester acid, oleyl acid
Phosphate, behenyl base phosphate ester acid, phenyl acid phosphate, nonyl phenyl phosphate ester acid, cyclohexyl phosphate ester acid, benzene
Oxygroup ethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol-A phosphate ester acid, dimethyl phosphate ester acid,
Diethyl phosphate ester acid, dipropyl phosphate ester acid, diisopropyl phosphate ester acid, dibutyl phosphate ester acid, dioctyl
Phosphate ester acid, two -2- ethylhexyl phosphate ester acids, didecyl phosphate ester acid, dilauryl phosphate ester acid, distearyl
The organic phosphoric acids such as base phosphate ester acid, diphenyl phosphate ester acid, dinonylphenyl phosphate ester acid；Sulfonium salt, benzothiazole
The heats such as salt, ammonium salt, phosphonium salt generate the raw drug of reagent (Re Suan development of acid) etc..These can be used alone or and with 2 kinds with
On.
From with the intermiscibility of (A) ingredient and (B) ingredient it is good from the viewpoint of, the preferably above-mentioned organic acid of (C) ingredient.Into
One step, from the viewpoint of rapidly-curable, preferably above-mentioned organic sulfonic acid and/or above-mentioned organic phosphoric acid；From same viewpoint
From the point of view of, particularly preferred organic sulfonic acid.
(C) content of ingredient is not particularly restricted, from the storage stability that can have both rapidly-curable and coating agent
From the viewpoint of, relative to the 100 weight % of total solid content of coating agent, preferably 1-10 weight % or so, more preferably 2-8
Weight % or so.In addition, from the viewpoint of equally, relative to total 100 parts by weight of (A) ingredient and (B) ingredient, preferably
2-25 parts by weight or so, more preferably 3-10 parts by weight or so.
Coating agent of the invention can also further containing can with (A) ingredient formed cross-linked structure polyalcohol (D) (with
It is known as (D) ingredient down).(D) there are more than two hydroxyls as long as ingredient is in a molecule, it can not particularly restrictedly
Use various well known substances.Specifically, can enumerate: ethylene glycol, 2- methyl-1,3-propanediol, 1,6- hexylene glycol, 3- first
Base -1,5- pentanediol, neopentyl glycol, 2- methyl-1,5- pentanediol, 2,2- diethyl -1,3- propylene glycol, 1,9- nonanediol, 1,
The aliphatic diols such as 10- decanediol, butyl ethyl propylene glycol, butyl ethyl pentanediol；1,4 cyclohexane dimethanol etc. is alicyclic
Glycol；Trimethylolpropane, pentaerythrite, double trimethylolpropane, dipentaerythritol, dimer diol, hydrogenation dimer diol, three
The alkylene of poly- triol, hydrogenation trimerization triol, castor oil, castor-oil plant oils modified polyalcohol and bisphenol compound or derivatives thereof
Oxygen addition product etc..In addition, can also enumerate: polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol (ア
Network リ Le Port リ オ ー Le) and the polymer polyatomic alcohols such as polyolefin polyhydric alcohol.These can be used alone, can also combine 2 kinds with
On.In addition, (D) ingredient is different from above-mentioned (B) ingredient.
As the molecular weight of (D) ingredient, from the viewpoint of rapidly-curable be usually 60-3,000 or so, preferably
80-2,000 or so, more preferably 100-1,500.In addition, the molecular weight of (D) ingredient be formula weight (formula weight) or number-average molecular weight,
Refer to formula weight in the case where that can determine molecular weight with the formula weight of chemical formula.Number-average molecular weight is using solidifying in the same manner as described above
The polystyrene scaled value that glue penetration chromatography obtains.As the hydroxyl value of (D) ingredient, from the viewpoint of rapidly-curable preferably
For 50-2,000mgKOH/g or so, more preferably 100-1,500mgKOH/g or so.
In coating agent of the invention, the content ratio of (A) ingredient and (D) ingredient is not particularly restricted, from can be simultaneous
From the viewpoint of the solvent resistance for having rapidly-curable and cured film, weight ratio [(A)/(D)] is preferably the left side 90/10-30/70
The right side, more preferably 80/20-40/60 or so.In addition, the content of (D) ingredient is not particularly restricted, it is quickly solid from that can have both
From the viewpoint of the solvent resistance of the property changed and cured film, relative to the 100 weight % of total solid content of coating agent, preferably 10-
60 weight % or so.
Organic solvent (E) (hereinafter referred to as (E) ingredient) can also be contained in coating agent of the invention.Specifically, for example
It can enumerate: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetone, ethyl acetate, butyl acetate, toluene, dimethylbenzene, isopropanol, ethyl alcohol, fourth
Alcohol etc., can be used more than one.Wherein, it from the viewpoint of dissolubility, is preferably chosen from by methyl ethyl ketone, methyl-isobutyl
At least one of ketone, isopropanol, ethyl acetate and group of toluene composition.
(E) content of ingredient is not particularly restricted, it is usually preferred in the solid component concentration for making coating agent of the invention
To contain in the range of 1-50 weight % or so.By for such numberical range, the appearance of film of cured film, coating agent are consolidated
The property changed and cured film become good to the balance of the adherence of plastic foil (especially polyethylene terephthalate film).
The manufacturing method of coating agent of the invention is not particularly restricted, can enumerate the method for mixing above-mentioned each ingredient.
Order by merging as each ingredient is not particularly restricted, can be mixed from any ingredient.In addition, mixed method also not by
To being particularly limited to, the various well known methods such as stirring can be used.
It can according to need the various well known additives of cooperation in coating agent of the invention, such as adhesive, defoaming agent, anti-
Rotten agent, curing agent, pH adjusting agent, antioxidant, pigment, dyestuff, lubricant, levelling agent (レ ベ リ Application グ drug), is prevented antirust agent
Adhesion agent (Block ロ ッ キ Application グ prevents drug), conductive agent etc..It is not particularly restricted as the adhesive, it can enumerate: phenolic aldehyde tree
Rouge (Off ェ ノ ー Le resin), epoxy resin, Lauxite (urea resin), polyurethane resin, alkyd resin etc..It is solid as this
Agent can be enumerated: Isocyanates curing agent, epoxies curing agent, aziridines curing agent, carbodiimide class curing agent,
Oxazoline class curing agent etc..
Stripping film of the invention is the product at least on single side with the peeling layer formed by coating agent of the invention, can
With by being coated with coating agent of the invention on various well known base material films, reheating or drying etc. obtain its solidification.
It as base material film, such as can enumerate: polycarbonate, polymethyl methacrylate, polystyrene, poly terephthalic acid
Glycol ester (PET), polyimides, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, ABS
The film that the plastics such as resin, AS resin, norbornene resin are formed.The base material film, which can be, is surface-treated that (corona is put
Electricity etc.) film.Wherein, from the viewpoint of the performances such as the transparency, dimensional stability, mechanical property, chemical-resistant, preferably
Polyethylene terephthalate.These plastic foils can also be arranged by thermohardening type stripping of the invention on its one or both sides
The layer formed from the coating agent other than coating agent.
Above-mentioned peeling layer (cured film) be by thermohardening type removing coating agent of the invention so that after solidifying with a thickness of
0.01-10 μm or so, preferably 0.1-5 μm or so of mode is coated on various substrates and heated, dried etc. and obtaining
Peeling layer.
Coating method is not particularly restricted, can be using various well known methods.Specifically, can for example enumerate:
Roll coater, reverse roll coater, gravure coater, blade coating machine, metering bar coater etc..
Heating, drying condition be not particularly restricted.Coating agent of the invention is usually in 90-130 DEG C or so and 30 seconds -2
Minute or so solidification, it is contemplated that general film formation condition is usually 150-190 DEG C or so and -5 minutes or so 1 minute, can
To say that coating agent of the invention solidifies at relatively low temperatures.Therefore, which is suitable for the modeling for being easy to deform by heat
Film is expected, especially suitable for polyethylene terephthalate film.
It as the purposes of stripping film of the present invention, such as can enumerate: ceramic green sheet, synthetic leather, decorative panel, carbon fibre initial rinse
The manufacturing processes such as material, printed base plate stripping film；And transfer correlated product stripping film；The bonding such as polarizing film or phase plate
Layer protection stripping film etc..
Embodiment
Below by way of reference implementation example and comparative example to present invention progress more specific description, but the present invention is not limited to
These embodiments.In each embodiment and comparative example, unless otherwise indicated, part and % are on the basis of weight.
<preparation of thermohardening type removing coating agent>
Embodiment 1
It will be as ニ カ ラ ッ Network MX-45 (full ether type methylation butylated melamine resins, (strain) three He of (A) ingredient
Chemistry manufacture) 99 parts by weight, as the PHF-33 of (B) ingredient, (12- hydroxy stearic acid self condenses object, her rattan liquefaction (strain) system
Make) 1 parts by weight, 4 parts by weight of the p-methyl benzenesulfonic acid cooperation as (C) ingredient, it is used into 333 parts by weight of toluene, 83 weight of isopropanol
Part dilution is measured, solid component concentration is modulated to 20%, obtains thermohardening type removing coating agent (hereinafter also referred to coating agent).
Embodiment 2- embodiment 13, comparative example 1- comparative example 6
Other than it will form the composition for being changed to table 1, with similarly to Example 1 the step of manufacture.
<production of stripping film>
By the coating agent of embodiment 1 be coated on polyethylene terephthalate film (50 μm of film thickness, the manufacture of eastern レ (strain),
" Le ミ ラ ー T60 ") on, make 1 μm of cured film, is made it dry at 120 DEG C 1 minute, thus obtain stripping film.For other
The coating agent of embodiment and comparative example, also obtains stripping film in the same way.
(appearance of film)
In the above-mentioned production for the stripping film that embodiment 1 is related to, the appearance of cured film is observed, is commented according to following judgment criteria
Valence appearance of film.In the stripping film that other embodiments and comparative example are related to, also evaluated in the same way.
Zero: obtaining transparent smooth cured film.
×: cured film gonorrhoea；Or
There is dissolution to remain in coating agent, bumps are observed in cured film.
(solvent resistance)
With the cured film for the stripping film that the swab stick wiping embodiment 1 being immersed in methyl ethyl ketone is related to, measurement is revealed until substrate
Round-trip number until out, thus evaluates the solvent resistance of the cured film.The removing that other embodiments and comparative example are related to
Film also evaluates solvent resistance in the same way.
Zero: even if wiping 50 times or more, the surface of base material film (polyethylene terephthalate film) is not also exposed.
△: at wiping 10-49 times, the surface of base material film is exposed.
×: at wiping 1-9 times, the surface of base material film is exposed.
(peeling force)
Polyester binding adhesive tape (day east electrician (strain) manufactures, 31B adhesive tape: 25mm wide) crimping is fitted in reality with the roller of 2kg
In the cured film for applying the stripping film that example 1 is related to, saved 1 hour at 23 DEG C.Then, with 180 ° of angle, the stripping of 0.3m/min
The adhesive tape, power (N/25mm) needed for measurement removing are uncovered from speed.For the stripping film that other embodiments and comparative example are related to,
Also peeling force is measured in the same way.
The unit of use level is parts by weight in table 1.Abbreviation and annotation in table 1 is as described below:
(1) due to poor solvent resistance, the evaluation of peeling force is not carried out；
(2) since appearance of film is concave-convex or albefaction, the evaluation of solvent resistance and peeling force is not carried out.
(abbreviation and details of compound)
ニ カ ラ ッ Network MX-45: full ether type methylation butylated melamine resins, (strain) three and chemistry manufacture
サ イ メ Le 303LF: full ether type methylated melamine resins, オ Le ネ Network ス ジ ャ パ Application (strain) manufacture
PHF-33:12- hydroxy stearic acid self condenses object (number-average molecular weight 1,800), she manufactures rattan liquefaction (strain)
PCF-30: Castor Oil Fatty Acid self condenses object (number-average molecular weight 1,600), she manufactures rattan liquefaction (strain)
12- hydroxy stearic acid: she manufactures rattan liquefaction (strain)
Network ラ レ Port リ オ ー Le F-3010: polyester polyol (number-average molecular weight 3,000), (strain) Network ラ レ manufacture
Pripol2033: hydrogenation dimer diol (number-average molecular weight 540), ク ロ ー ダ ジ ャ パ Application (strain) manufacture
ピ ー ロ イ Le 1010S: chain alkyl side-chain polymer, ラ イ オ Application ス ペ シ ャ リ テ ィ ケ ミ カ Le
ズ (strain) manufacture
URIC F-97: castor-oil plant oils modified polyalcohol, she manufactures rattan liquefaction (strain).
Claims (10)
1. thermohardening type removes coating agent, the thermohardening type removing coating agent contains melamine resin (A), carbon atom number
The aliphatic hydroxyl carboxylic acid (b) of 12-24 self condenses object (B) and acid catalyst (C).
2. thermohardening type as described in claim 1 removes coating agent, wherein (A) ingredient contains from methylated melamine
And/or the structural unit of butylated melamines.
3. thermohardening type as claimed in claim 1 or 2 removes coating agent, wherein (B) ingredient is the aliphatic of carbon atom number 18
Hydroxycarboxylic acid self condenses object.
4. thermohardening type as claimed in any one of claims 1-3 removes coating agent, wherein relative to the removing coating agent
100 weight % of total solid content, the content of (B) ingredient is 1-50 weight %.
5. as thermohardening type of any of claims 1-4 remove coating agent, wherein (C) ingredient be organic sulfonic acid and/
Or organic phosphoric acid.
6. thermohardening type according to any one of claims 1 to 5 removes coating agent, wherein relative to the removing coating agent
100 weight % of total solid content, the content of (C) ingredient is 1-10 weight %.
7. as thermohardening type of any of claims 1-6 removes coating agent, wherein the thermohardening type removing coating
Agent also contains polyalcohol (D).
8. thermohardening type as claimed in claim 7 removes coating agent, wherein the weight ratio of (A) ingredient and (D) ingredient [(A)/
It (D)] is 90/10-30/70.
9. cured film and plastic foil comprising being formed by thermohardening type removing coating agent such as of any of claims 1-8
Stripping film.
10. stripping film as claimed in claim 9, wherein the plastic foil is polyethylene terephthalate film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017221510 | 2017-11-17 | ||
| JP2017-221510 | 2017-11-17 |
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| CN109796841A true CN109796841A (en) | 2019-05-24 |
| CN109796841B CN109796841B (en) | 2022-04-26 |
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| CN201811342829.4A Active CN109796841B (en) | 2017-11-17 | 2018-11-12 | Heat-curable release coating agent and release film |
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| Country | Link |
|---|---|
| JP (1) | JP7172468B2 (en) |
| CN (1) | CN109796841B (en) |
| TW (1) | TWI772554B (en) |
Cited By (2)
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|---|---|---|---|---|
| CN113185890A (en) * | 2020-01-29 | 2021-07-30 | 荒川化学工业株式会社 | Thermosetting release coating agent, cured product, thermosetting release film, and method for producing same |
| CN115772281A (en) * | 2021-09-07 | 2023-03-10 | 东丽尖端素材株式会社 | Release film |
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| JPH0987581A (en) * | 1995-09-27 | 1997-03-31 | Kansai Paint Co Ltd | Coating composition and coated metal sheet using the same |
| JP2010253384A (en) * | 2009-04-24 | 2010-11-11 | Nippon Paint Co Ltd | Method of forming laminated coating film and coated article |
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| CN115772281A (en) * | 2021-09-07 | 2023-03-10 | 东丽尖端素材株式会社 | Release film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019094483A (en) | 2019-06-20 |
| CN109796841B (en) | 2022-04-26 |
| JP7172468B2 (en) | 2022-11-16 |
| TWI772554B (en) | 2022-08-01 |
| TW201922975A (en) | 2019-06-16 |
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