CN109462992A - Carbamate system bonding agent, carbamate system bonding agent glycol composition, carbamate system bonding agent polyisocyantates composition, aforementioned carbamate system bonding agent solidfied material and laminate film - Google Patents
Carbamate system bonding agent, carbamate system bonding agent glycol composition, carbamate system bonding agent polyisocyantates composition, aforementioned carbamate system bonding agent solidfied material and laminate film Download PDFInfo
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- CN109462992A CN109462992A CN201780039001.9A CN201780039001A CN109462992A CN 109462992 A CN109462992 A CN 109462992A CN 201780039001 A CN201780039001 A CN 201780039001A CN 109462992 A CN109462992 A CN 109462992A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- 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
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
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- 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
- C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/06—Copolymers with vinyl aromatic monomers
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- 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
- C09J175/06—Polyurethanes from polyesters
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- 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
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Polyalcohol (A), polyisocyanates (B) and SP value in the group being made of polyester polyol, polyester polyether polyol, polyester polyurethane polyalcohol, polyether polyurethane polyalcohol and polyester polyether polyurethane polyalcohol is 20~32 (J/cm by a kind of carbamate system bonding agent3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value is used as essential component, and to contain aforementioned carboxylated compound (C) relative to the ratio that 100 mass parts of polyalcohol (A) are 0.01~1.5 mass parts.
Description
Technical field
The present invention relates to carbamate system bonding agent, the polyisocyanate mixtures for it, polyol blends and
Laminate film made of various films is laminated using the bonding agent.More specifically it is related to a kind of thin by being laminated various plastics
Film, metal evaporation film, aluminium foil etc. are mainly used for the laminated film when institute of the packaging materials such as food, drug, detergent to manufacture
The lamination bonding agent used.
Background technique
For packaging material for food, drug, daily necessities packaging material, by film substrate surface coating adhesive
Afterwards, evaporation drying removes solvent, the plural layers that the so-called dry lamination that Bian Jiare, crimping other materials side are laminated obtains
It is widely used since the arbitrary film of combination can be selected according to the required characteristic of each purposes.
The mainstream of bonding agent for above-mentioned dry lamination is two component type polyurethanes system bonding agents, is mainly
Have the polyol component of hydroxyl as host agent in macromolecule end, on the other hand, using polyisocyanates as curing agent.This
Place, foregoing polyols ingredient uses polyester polyol, polyester polyurethane polyalcohol, on the other hand, from the curing agent sheet
From the aspect of body plays a role as reactive diluent, toluene di-isocyanate(TDI) (TDI), '-diphenylmethane diisocyanate are used
(MDI), the various haplotype polyisocyanates such as isophorone diisocyanate (IPDI) are as aforementioned polyisocyanates.
However, using the amino used using above-mentioned polyester polyol, polyester polyurethane polyalcohol as host agent
When formic acid esters system bonding agent is packed for laminated film to prepare, the adhesive layer of plural layers is easy by the food as content
The etch of sour component, alkaline components Deng contained in and be destroyed.
Especially in recent years, having used the food packaging (snacks, frozen food etc.) of aluminium-vapour deposition film increased, right
When the sour components such as vinegar, free fatty acid contained in the food as content or basic food are packed, boiled
The disappearance of aluminium-vapour deposition layer, printed patterns disappearance or the thing that can see content can occur during being displayed in StoreFront after boiling sterilization processing
The problems such as example, is especially prominent.
Therefore, all the time, for example, the following patent document 1 discloses following technologies: as in food packaging multilayer
The lamination bonding agent of aluminium foil and un-stretched polypropylene film in film, by using by making polymer polyatomic alcohol carry out benzene second
The carbamate system bonding agent that polyalcohol obtained from alkene-is maleic anhydride modified and polyisocyanates are constituted, so as to improve more
The compatibility of first alcohol component and polyisocyanate component prevents bonding caused by being originated from the vinegar of content, free fatty acid
The disappearance of layer.
However, the dosage of phenylethylene-maleic anhydride is more, and relative to polymerization for the bonding agent recorded in patent document 1
100 mass parts of object polyalcohol are using 6 mass parts or so, therefore the viscosity of bonding agent itself increases and carries secretly in lamination process empty
Gas etc. reduces film appearance, and furthermore adhesive layer becomes hard crisp, is as a result unable to get long-term adhesive strength, when used for a long time without
Method avoids the disappearance of aforementioned aluminium-vapour deposition layer.
Existing technical literature
Patent document
Patent document 1: No. 3206946 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
Therefore, the problem to be solved by the present invention is that provide bonding agent, the bonding agent can be used for host agent or curing agent and
The plural layers of long-time stability obtained from lamination process and excellent appearance are carried out using the bonding agent, the bonding agent is used
In the lamination of the metal coverings such as laminated film, particularly aluminium foil or aluminium-vapour deposition film and resin film, therefore due to excellent in workability
The appearance of obtained laminated film is good, furthermore long-term bonding agent excellent strength, metal evaporation film is thin as substrate
The disappearance of metal vapor deposition layer can chronically be inhibited when film.
The solution to the problem
The inventors of the present invention have made intensive studies to solve aforementioned problems, as a result, it has been found that: for polyalcohol/polyisocyanate cyanogen
The bonding agent of acid esters, by the way that there is spy to use relative to the ratio that 100 mass parts of foregoing polyols are 0.01~1.5 mass parts
The carboxylated compound of fixed SP value as additive component, thus become plural layers long-term excellent in stability and by
In showing good processability and the appearance of the plural layers also excellent bonding agent, so that complete the present invention.
That is, the present invention provides a kind of carbamate system bonding agent, contain: selected from by polyester polyol (a1), polyester
Polyalcohol (A), polyisocyanic acid in the group of urethane polyol (a2) and polyether urethane polyalcohol (a3) composition
Ester (B) and SP value are 20~32 (J/cm3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value, with relative to
100 mass parts of polyalcohol (A) are that the ratio of 0.01~1.5 mass parts contains aforementioned carboxylated compound (C).
The present invention also provides a kind of carbamate system bonding agent glycol compositions, contain: selected from more by polyester
Polyalcohol in the group of first alcohol (a1), polyester urethane polyalcohol (a2) and polyether urethane polyalcohol (a3) composition
(A) and SP value is 20~32 (J/cm3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value, relative to more
First 100 mass parts of alcohol (A) are that the ratio of 0.01~1.5 mass parts contains aforementioned carboxylated compound (C).
The present invention also provides a kind of carbamate system bonding agent polyisocyantates compositions, contain polyisocyanates
(B) and SP value is 20~32 (J/cm3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value.
It is made of solidifying aforementioned carbamate system bonding agent the present invention also provides a kind of solidfied material.
It is that aforementioned carbamate system bonding agent is coated on first base material is thin the present invention also provides a kind of laminate film
Film, be then laminated on coated face the second base film make the adhesive layer solidify made of.
The effect of invention
In accordance with the invention it is possible to which the appearance for providing excellent in workability and laminated film is good and long-term adhesive strength
Excellent bonding agent, its host agent or curing agent and long-time stability obtained from lamination process and outer have been carried out using the bonding agent
Excellent plural layers are seen, the bonding agent is for laminated film, particularly the metal coverings such as aluminium foil or aluminium-vapour deposition film and resin
The lamination of film.
Specific embodiment
As previously mentioned, carbamate system bonding agent of the invention is characterized in that, will selected from by polyester polyol (a1),
Polyalcohol (A), polyisocyanate in the group of polyester urethane polyalcohol (a2) and polyether urethane polyalcohol (a3) composition
Cyanate (B) and SP value are 20~32 (J/cm3)1/2And carboxylated compound (C) conduct of 250~1000mgKOH/g of acid value
Essential component, and it is aforementioned carboxylated to contain relative to the ratio that 100 mass parts of polyalcohol (A) are 0.01~1.5 mass parts
It closes object (C).Above-mentioned carbamate system bonding agent is two component type bonding agents of polyalcohol (A)/polyisocyanates (B), aforementioned
Carboxylated compound (C) can by with used in the form of glycol composition made of foregoing polyols (A) compounding or can be with
It is used with the form of polyisocyantates composition made of aforementioned polyisocyanates (B) compounding.Alternatively, using can be with when bonding agent
It is compounded simultaneously when being compounded polyalcohol (A) and polyisocyanates (B).
It is aforementioned to be used relative to the ratio that 100 mass parts of polyalcohol (A) are 0.01~1.5 mass parts in the present invention
Carboxylated compound (C) is extremely important.When the dosage of aforementioned carboxylated compound (C) is lower than 0.01 mass parts, no Faxian
Reveal the effect that layering is prevented by compounding carboxylated compound (C) bring, in addition, when more than 1.5 mass parts, adhesive layer sheet
Body becomes hard crisp, is unable to get long-term adhesive strength, such as will receive content in the case where having used metal evaporation film
Contained in etch caused by acid, alkali and cause the disappearance that layer is deposited, the poor in processability and film appearance when furthermore coating are poor.
As previously mentioned, polyalcohol (A) used herein is selected from by polyester polyol (a1), polyester urethane polyalcohol
(a2) and polyether urethane polyalcohol (a3) composition group.The carbamate system bonding being made of these polyol components
Agent shows excellent adhesive property, processability, on the other hand, the case where in content including acidic materials or alkaline matter
Lower adhesive layer is more easily damaged, and additive is used as by using carboxylated compound above-mentioned (C), so as to be effectively prevented
The disappearance of the adhesive layer as caused by acidic materials or alkaline matter.
For constituting the polyester polyol (a1) of above-mentioned polyalcohol (A), it can specifically enumerate: make aliphatic polyol
Polyester polyol obtained from reacting with aliphatic polycarboxylic acid (a1-1) keeps aliphatic polyol and aromatic polycarboxylic acid anti-
Polyester polyol obtained from answering (a1-2) and as obtained from the ring-opening polymerization of aliphatic cyclic ester compounds
The polyester polyol (a1-3) of the reactant of polyester and aliphatic polyol.
Herein, the aliphatic polyol as the raw material as polyester polyol (a1-1)~(a1-3), can enumerate: second
Glycol, propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methyl-1 are 5- pentanediol, 1,6-HD, new
Pentanediol, methyl pentanediol, dimethylbutadio, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyl
The aliphatic diols such as glycol, tripropylene glycol, 1,4- cyclohexanediol, 1,4 cyclohexane dimethanol, triethylene glycol；Glycerol, three hydroxyl first
The aliphatic alcohol of the trifunctionals such as base propane, pentaerythrite or tetrafunctional；Two polyalcohols；As ethylene oxide, propylene oxide, epoxy fourth
Aliphatic poly ethoxylated polyhydric alcohol of the ring-opening polymerization polymer of the alkylene oxides such as alkane, epoxychloropropane, tetrahydrofuran, 7-oxa-bicyclo[4.1.0 etc..
On the other hand, the aliphatic polycarboxylic acid as the raw material as polyester polyol (a1-1), can enumerate: amber
Acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3- cyclopentane dicarboxylic acid, 1,4- ring
Hexane dicarboxylic acid, dimeric dibasic acid etc. can be enumerated as the aromatic polycarboxylic acid of the raw material as polyester polyol (a1-2):
Terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalene dicarboxylic acids, 2,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, naphthalenedicarboxylic acid, xenyl
Bis- (phenoxy group) ethane-p, p '-dicarboxylic acids of dicarboxylic acids, 1,2- etc..
In addition, the aliphatic cyclic ester compounds as the raw material as foregoing polyester polyols (a1-3), can enumerate:
Propiolactone, butyrolactone, 6-caprolactone, σ-valerolactone, Beta-methyl-σ-valerolactone etc..
The polyester polyol (a1) of detailed description above strong, content resistance from the patience to acidic materials, alkaline matter
From the aspect of excellent, number-average molecular weight (Mn) is preferably that 3000~5000, weight average molecular weight (Mw) is preferably 8000~15000
Range.In addition, hydroxyl value be 3~50mgKOH/g range the case where from the wetability of substrate it is excellent from the aspect of be preferred.
It should be noted that number-average molecular weight (Mn) or weight average molecular weight (Mw) are by following conditions in the present invention
The value that gel permeation chromatography (GPC) measures.
Measurement device: TOSOH CORPORATION manufactures HLC-8220GPC
Column: TOSOH CORPORATION manufactures TSK-GUARDCOLUMN SuperHZ-L+TOSOH CORPORATION system
Make SuperHZM-M × 4 TSK-GEL
Detector: RI (differential refractometer)
Data processing: TOSOH CORPORATION manufactures Multi-Station GPC-8020modelII
Determination condition: 40 DEG C of column temperature
Solvents tetrahydrofurane
Flow velocity 0.35ml/ minutes
Standard: monodisperse polystyrene
Sample: the tetrahydrofuran solution for being calculated as 0.2 mass % with resin solid content conversion is carried out with microfilter
Filter resulting substance (100 μ l)
Then, polyester polyurethane polyalcohol (a2) is to make polyester polyol above-mentioned (a1) by polyisocyanates
There is the polyalcohol of urethane bond obtained from modification, in molecular structure.
It as polyisocyanates used herein, can enumerate: isophorone diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (rings
Hexyl isocyanates), 1,3- (isocyanatomethyl) hexamethylene etc. in molecular structure with the polyisocyanate cyanogen of ester ring type structure
Acid esters；The straight-chains such as 1,6- hexamethylene diisocyanate, lysine diisocyanate, trimethyl hexamethylene diisocyanate
Aliphatic polyisocyante；Toluene di-isocyanate(TDI), xylylene diisocyanate, '-diphenylmethane diisocyanate, 1,5- naphthalene
Aromatic polyisocyanates such as diisocyanate, triphenylmethane triisocyanate etc..
Herein, good, simultaneously from initial cementability is become as polyester polyurethane polyalcohol (a2) in the present invention
And heat resistance, water resistance, oil resistivity, the angle of hot water resistance and the excellent bonding agent of alkali resistance are set out, and are had containing being originated from two
The side chain of the alkyl chain of 6 or more the carbon number of the polyacids or two polyalcohols and branch point concentration of the side chain is relative to adhesive composite
1 gram of solid component for the polyester polyurethane polyalcohol (a2-1) more than 0.2 mM (after, mmol/g) be preferred
's.
Herein, dimeric dibasic acid is that the long-chain unsaturated fatty acids such as oleic acid, linoleic acid pass through diels-Alder (Diels-
Alder) product obtained from type dimerization has the various objects such as the substance for adding hydrogen on unsaturated bond and obtaining its saturation
Matter, such as can enumerate by the trimer acid 0 of dimeric dibasic acid 70~98 the mass % and C54 of 0~5 weight %, C36 of monocarboxylic acid of C18
The substance that~30 weight % are constituted.In addition, two polyalcohols are obtained from restoring above explained dimeric dibasic acid.
In addition, the variation of dynamic viscoelastic rate is small and can not obtain when the branch point concentration of the side chain of 70 or more molecular weight is few
To desired physical property, therefore the branch point concentration preferably comprises 0.2mmol/g or more relative to bonding agent solid component.
From the aspect of adhesive strength, mobility, the polyester urethane polyalcohol (a2-1) of detailed description above
The range that range that number-average molecular weight (Mn) is preferably 8000~15000, weight average molecular weight (Mw) are preferably 25000~35000.
In addition, from the wetability of substrate it is excellent from the aspect of, hydroxyl value be 2~15mgKOH/g range be preferred.
For polyester polyurethane polyalcohol (a2), in addition to aforementioned polyester polyurethane polyalcohol (a2-1) it
Outside, as raw material alcohol component, the aliphatic alcohol of aforementioned aliphatic diol and trifunctional or tetrafunctional is applied in combination, as raw material carboxylic
The long-chain fat race dicarboxylic acids and fragrance of the C9-C12 such as azelaic acid, decanedioic acid (c10), dodecanedicarboxylic acid is applied in combination in sour component
Race's dicarboxylic acids reacts polyester obtained from esterification occurs with the aforementioned polyisocyanates with ester ring type structure and obtains
Polyester polyurethane polyalcohol (a2-2) therefore can be used for from the flexibility with excellent adhesive strength and appropriateness it is resistance to
It is preferred from the aspect of the excellent retort pouch (retort pouch) of steaming property.
From the aspect of aforementioned resistance to steaming property, the preferred number of the polyester urethane polyalcohol (a2-2) of detailed description above is equal
The range that molecular weight (Mn) is 7000~10000, weight average molecular weight (Mw) is 25000~40000.In addition, from the profit with substrate
It is moist it is excellent from the aspect of, hydroxyl value be 2~15mgKOH/g range be preferred.
Then, polyether polyurethane polyalcohol (a3) can enumerate the polyether polyol containing urethane bond,
It has polyether polyol and then has carried out the tree that molecular weight obtains with aforementioned fragrance race or aliphatic polyisocyante
Rouge structure, the polyether polyol are as follows: make ethylene glycol, propylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 3- first
Base -1,5- pentanediol, 1,6-HD, neopentyl glycol, methyl pentanediol, dimethylbutadio, butyl ethyl propylene glycol, diethyl
Glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, double hydroxyl-oxethyl benzene, 1,4- cyclohexanediol, 1,4- hexamethylene
Glycol such as alkane dimethanol, triethylene glycol etc. are in the presence of polymerization initiator and ethylene oxide, propylene oxide, epoxy butane, benzene
Polyether polyol made of the alkylene oxides addition polymerization such as hexadecyl ethylene oxide, epoxychloropropane, tetrahydrofuran, 7-oxa-bicyclo[4.1.0.
The polyether polyurethane polyalcohol (a3) of detailed description above can cope with high speed lamination side from mobility is excellent
Face consideration, the range that preferred number average molecular weight (Mn) is 4000~6000, the model that weight average molecular weight (Mw) is 14000~20000
It encloses.In addition, from the wetability of substrate it is excellent from the aspect of, hydroxyl value be 3~25mgKOH/g range be preferred.
Then, it is to be used for that SP value, which is the carboxylated compound (C) of 13.00~15.00 and 250~1000mgKOH/g of acid value,
Show lamination strength, particularly the ingredient with metal steam surfacing, the excellent adhesive property of metallic film.
Herein, SP value be using Fedors calculation according to following formulas by chemical structure cohesive energy densities with
The value (δ) that molar volume is calculated
Herein, the calculation of Fedors is calculation shown in following documents.
[document]
R.F.Fedors, Polym.Eng.Sci., 14 (2), 145-154,1974
In formula, Ecoh indicates to constitute the cohesive energy densities of each structural unit of chemical structure.For example,-CH2It is
4940J/ moles ,-CH3For 4710J/ moles ,-CO- be 17360J/ moles ,-COO- is 18000J/ moles ,-COOH is
27630J/ moles ,=CH- be 4,310J/ moles ,-CH < for 3430J/ moles ,-OH is 29800J/ moles ,-O- is 3350J/
Mole etc..
On the other hand, V is the molar volume for constituting each structural unit of chemical structure, for example,-CH2It is
16.1cm3/ mole ,-CH3For 33.5cm3/ mole ,-CO- be 10.8cm3/ mole ,-COO- be 18.0cm3/ mole ,-COOH be
28.5cm3/ mole ,=CH- be 13.5cm3/ mole,-CH < for -1.0cm3/ mole ,-OH be 10.0cm3/ mole ,-O- be
3.8cm3/ mole etc..
The SP value of the carboxylated compound as used in the present invention (C) is 20~32 (J/cm3)1/2, therefore with it is aforementioned more
First alcohol (A) or polyisocyanates (B) it is excellent in compatibility, can effectively exclude acidic materials, alkaline matter by content
The influence of generation.
In the present invention, due to aforementioned carboxylated compound (C) acid value be 250~1000mgKOH/g range, with
The excellent adhesion of substrate, the especially excellent adhesion with metallic foil substrates or metal evaporation surface.
Herein, it as aforementioned carboxylated compound (C), can specifically enumerate: aromatic vinyl and maleic anhydride
Copolymer (c1), aliphatic carboxylic acid (c2) and tetrabydrophthalic anhydride skeleton (c3) containing hydroxyl.
For aforementioned fragrance race ethylene/copolymer-maleic anhydride (c1), the aromatic vinyl/copolymer-maleic anhydride is constituted
(c1) the case where monomer composition ratio (molar ratio of [aromatic vinyl/maleic anhydride]) is in the range of 1.5/1~5/1, from
It is excellent in compatibility with foregoing polyols (A), it is strong especially excellent lamination will can also to be shown after bonding agent long-term preservation
It is preferred from the aspect of degree.In addition, weight average molecular weight is preferred especially from from the aspect of the compatibility of polyalcohol (A)
For 1000~4000 range, from the aspect of bonding agent intensity, anti-PAA dissolution, acid value is preferably 0.1~20mgKOH/g's
Range.
As the aromatic vinyl for constituting above-mentioned aromatic vinyl/copolymer-maleic anhydride (c1), can specifically enumerate
Out: styrene, α-methylstyrene, divinylbenzene etc., wherein from the side excellent in compatibility with aftermentioned polyisocyanates (B)
Face consideration, optimization styrene.
For the aforementioned SP value of above-mentioned aromatic vinyl/copolymer-maleic anhydride (c1), by calculating due to virtue
The respective SP value (δ) of the structural unit (s) of fragrant race's ethylene and the structural unit (m) due to maleic anhydride, according to aromatic series
Ethylene and maleic anhydride there are ratios to be calculated.For example, the molar ratio of aromatic vinyl and maleic anhydride is 1:1's
The case where copolymer, as long as simply calculating the SP value of the structural unit (s) due to aromatic vinyl and due to Malaysia
The molar ratio of the sum of SP value of the structural unit (m) of acid anhydrides, aromatic vinyl and maleic anhydride is the feelings of the copolymer of 2:1
Condition, as long as by the SP value of structural unit (s) multiplied by 2, and be added with the SP value of structural unit (m).
Specifically the case where 1:1 (molar ratio) reactant of phenylethylene/maleic anhydride, SP value is 31.4 (J/cm3)1/2。
Then, the aliphatic carboxylic acid (c2) containing hydroxyl used as aforementioned carboxylated compound (C), can enumerate:
2,2- bis- (methylol) propionic acid [28.7 (J/cm of SP value3)1/2, acid value 414-418mgKOH/g], (methylol) butyric acid of 2,2- bis- SP
27.4 (J/cm of value3)1/2, acid value 374-378mgKOH/g] etc..
Then, the compound containing tetrabydrophthalic anhydride skeleton used as aforementioned carboxylated compound (C)
(c3) it can enumerate: tetrahydrofuran [27.7 (J/cm of SP value3)1/2, acid value 675mgKOH/g], shown in following structural formula 1,
3a, 4,5,7a- tetrahydro -7- methyl -5- (tetrahydro -2,5- dioxo -3- furyl) iso- benzofuran two of -1,3-
Ketone [29.1 (J/cm of SP value3)1/2, acid value 849mgKOH/g].
Herein, for aforementioned fragrance race ethylene/copolymer-maleic anhydride (c1), because to as dry lamination bonding agent
General solvent ethyl acetate shows excellent dissolubility when use, therefore is preferably compounded into as in dry lamination bonding agent
Host agent foregoing polyester polyols (a1), polyester urethane polyalcohol (a2) or polyether urethane polyalcohol
(a3) it is used in the form of ethyl acetate solution in.
In addition, the aliphatic carboxylic acid (c2) containing hydroxyl polyether urethane polyalcohol (a3) is shown it is excellent
Dissolubility, therefore be compounded in polyether urethane polyalcohol (a3) and made of being dissolved in ethyl acetate by being used as
Dry lamination host agent polyol component and use, so as to prepare and high speed be laminated corresponding bonding agent, examined from this respect
Worry is preferred.
In addition, for the aforementioned compound (c3) containing tetrabydrophthalic anhydride skeleton because for polyalcohol (A),
Polyisocyanates (B) has good compatibility, therefore dry lamination bonding agent, no-solvent type bonding agent can be made to make
With, such as the curing agent component of dry lamination bonding agent, used by being compounded in polyisocyanates (B), thus
The present invention can be made to correspond to multiple product to change, be preferred from this viewpoint.
Then, polyisocyanates (B) used in the present invention can for example enumerate: toluene di-isocyanate(TDI), diphenyl-methane
Diisocyanate, 1,5- naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate etc. are in molecule knot
With the polyisocyanates of aromatic structure in structure；Isophorone diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanic acid
Ester), 1,3- (isocyanatomethyl) hexamethylene etc. in molecular structure with the polyisocyanates of ester ring type structure；1,6- six
The straight-chains aliphatic polyisocyanate such as methylene diisocyanate, lysine diisocyanate, trimethyl hexamethylene diisocyanate
Cyanate；For various polyisocyanates above-mentioned, rubbed relative to 1 mole of trimethylolpropane with diisocyanate cpd 3
Adduct type polyisocyanates obtained from your ratio addition；Made relative to 3 moles of diisocyanate with 1 mole of water of ratio
Biuret form polyisocyanates or the isocyanide urea as obtained from the trimerizing of diisocyanate cpd obtained from it is reacted
Acid esters type polyisocyanates；Make polyisocyanates and polyester polyol, polyether polyol or is reacted in turn with low molecular polylol
Obtained from polyurethanes polyisocyanate compound (b3) etc..
Herein, the polyester polyol as the raw material as polyurethanes polyisocyanate compound (b3), can arrange
Polyester polyol above-mentioned (a1) is enumerated, as polyether polyol, can be enumerated: ethylene glycol, propylene glycol, 1,3-PD, 1,
4- butanediol, 1,5- pentanediol, 3- methyl-1,5- pentanediol, 1,6-HD, neopentyl glycol, methyl pentanediol, dimethyl butyrate
Glycol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4- hexamethylene two
The aliphatic diols such as alcohol, 1,4 cyclohexane dimethanol, triethylene glycol.
Especially as solvent type adhesive in these polyisocyanates (B), and adhesive strength excellent from curability is good
From the aspect of good, preferably: the urea acid esters body of the polyisocyanates in molecular structure with ester ring type structure；Relative to three hydroxyl first
The adduct type polyisocyanates of structure made of 3 moles of xylylene diisocyanate of base propane 1 mole of addition: relative to
Adduct type polyisocyanates made of 3 moles of toluene di-isocyanate(TDI) of trimethylolpropane 1 mole of addition；Methylene two is different
The polypropylene glycol modified object of cyanate.
As previously mentioned, the carbamate system bonding agent of the invention being made of each ingredient being described in detail above can be made
For solvent type adhesive or as no-solvent type bonding agent come using.
Used solvent when for using as solvent type adhesive can be used in manufacture polyalcohol (A) and polyisocyanate
Cyanate (B) Shi Zuowei reaction medium, and then in coating as substance used in diluent.It is molten as what can be used herein
Agent, such as can enumerate: the esters such as ethyl acetate, butyl acetate, cellosolve acetate；Acetone, methyl ethyl ketone, isobutyl ketone, ring
The ketones such as hexanone；The ethers such as tetrahydrofuran, dioxane；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Methylene chloride, dichloro
The halogenated hydrocarbons such as ethane；Dimethyl sulfoxide, dimethyl sulfonamide etc..It is excellent from the aspect of being easy from recycling/recycling in these
Choosing uses ethyl acetate or methyl ethyl ketone.
As previously mentioned, carbamate system bonding agent of the invention is the carbamate system bonding of two curing components types
Agent can be used in the form of following: aforementioned carboxylated compound (C) being compounded in polyalcohol made of in polyalcohol (A) in advance
Composition (X), or aforementioned carboxylated compound (C) is compounded in the combination of polyisocyanates made of in polyisocyanates (B)
Object (Y).
That is, the case where solvent type two component types carbamate system bonding agent, it can be by glycol composition (X) conduct
Two component host agents and by aforementioned polyisocyanates (B) as curing agent come using；Alternatively, can be by foregoing polyols (A) conduct
Host agent and by aforementioned polyisocyanates composition (Y) as curing agent come using.
It on the other hand, can be by aforementioned polyisocyanate cyanogen the case where two component type carbamate system bonding agent of no-solvent type
Acid ester composite (Y) be used as host agent, and by foregoing polyols (A) as curing agent come using；Or it can be by aforementioned polyisocyanate cyanogen
Acid esters (B) as host agent and by glycol composition (X) as curing agent come using.
Herein, as previously mentioned, foregoing polyols composition (X) is by foregoing polyols (A) and aforementioned carboxylated compound (C)
As essential component, the case where solvent type adhesive, and then organic solvent can be used.
On the other hand, polyisocyantates composition (Y) is by aforementioned polyisocyanates (B) and aforementioned carboxylated compound (C)
As essential component, the case where solvent type adhesive, and then organic solvent can be used.
As previously mentioned, carbamate system bonding agent of the invention may be used as solvent type bonding agent or solvent-free
The bonding agent of type, it is excellent from long-term storing stability and it is operational it is good from the aspect of, be preferably used as solvent type bonding agent.This
Place, has above-mentioned host agent and curing agent with aforementioned to prepare solvent type two component types carbamate system bonding agent
Solid component is adjusted to 50~80 mass % respectively by solvent, when in use in the state that two components are compounded and then according to need
Organic solvent is added, lamination process when being finally made the range of 20~40 mass % of solid component is excellent, from this respect
Consideration is preferred.
In the present invention, in the case where aforementioned carboxylated compound (C) is used as foregoing polyols composition (X) or use
It is relative to aforementioned by making the use ratio of aforementioned carboxylated compound (C) in the case where making polyisocyantates composition (Y)
100 mass parts of polyalcohol (A) are the ratio of 0.01~1.5 mass parts, so that processability when making lamination process is good and obtains
The appearance of the laminate film arrived is good, is furthermore possible to prevent the etch of acid, alkali from content for a long time.
For carbamate system bonding agent of the invention, the isocyanate group in polyisocyanates (B) is relative to polynary
When the range that the equivalent proportion (isocyanate group/hydroxyl) of the hydroxyl in alcohol (A) is 1.5~2.5, intensity/flexibility of adhesive layer
In the range of appropriateness, it is excellent from this viewpoint that initial bond strenght, long-term adhesive strength and then laminated appearance are good
Choosing.
Therefore, the use ratio or polyalcohol (A) and polyisocyanate of glycol composition (X) and aforementioned polyisocyanates (B)
The use ratio of cyanate compositions (Y) range that desirably aforementioned equivalent proportion (isocyanate group/hydroxyl) is 1.5~2.5.
By being further compounded aliphatic cyclic amide compound in carbamate system bonding agent of the invention, thus
Dissolution of the harmful low molecule chemical substance to content representated by aromatic amine in laminate packaging body can be effectively inhibited.
For above-mentioned aliphatic cyclic amide compound, any that can be compounded in glycol composition (X) and polyisocyanates (B)
In kind or it is compounded in any in polyalcohol (A) and polyisocyantates composition (Y) or is being coated as the 3rd ingredient
Shi Jinhang is compounded to use.
Aliphatic cyclic amide compound used herein can for example enumerate: δ-valerolactam, epsilon-caprolactams, ω-
Oenantholcatam, η-spicy inner formyl amine, beta-propiolactone etc..The excellent effect reduced in these from the amount of dissolution of low molecule chemical substance
From the aspect of, preferred epsilon-caprolactams.In addition, its compounding amount is preferred: relative to 100 mass parts of glycol composition (X), with
The range mixed aliphatic cyclic amide compound of 0.1~5 mass parts.
Carbamate system bonding agent of the invention, which can according to need, is applied in combination pigment.As the face that can be used at this time
Material, is not particularly limited, such as can enumerate: recording in the annual version (Japanese coating industry can compile) of coating raw material brief guide 1970
Extender pigment, white pigments, mineral black, gray paint, red pigment, dark brown pigment, viridine green, blue pigment, metal powder face
The organic pigments such as material, luminous pigment, pearl pigment, inorganic pigment and then plastic pigment etc..As the specific of these colorants
Example can enumerate various substances, as organic pigment, such as can enumerate: benzidine yellow, everbright fast yellow, pigment red 4 R etc., various
Insoluble azo colour；The insoluble azo pigments such as paratonere C, CARMINE 6B, purplish red 10；Phthalocyanine blue, phthalocyanine green etc. are various
(copper) phthualocyanine pigment；The various dyeing lakes containing chlorine such as rhodamine color lake, Methyl Violet Lake；Quinoline color lake, fast blue etc. are various
Mordant dye system pigment；Anthraquione pigmentss, thioindigo system pigment, purple cyclic ketones system pigment etc. are various to build dye dyestuff system pigment；It is fresh expensive
The various quinacridone pigments such as the red B of color；The various dioxazine pigments such as dioxazine violet；The various condensation azo face such as chromophyll
Material；Nigrosine etc..
It as inorganic pigment, such as can enumerate: such as various chromate of chrome yellow, zinc chromate, molybdate orange；It is Prussian blue etc.
Various ferrocyanides close object；The various metals such as titanium oxide, zinc white, Ma Pi Kehuang, iron oxide, Indian red, chrome oxide green, zirconium oxide
Oxide；The various sulfide such as cadmium yellow, cadmium red, mercuric sulphide or selenides；The various sulfate such as barium sulfate, lead sulfate；Calcium silicates,
The various silicates such as ultramarine；The various carbonate such as calcium carbonate, magnesium carbonate；The various phosphate such as cobalt violet, manganese violet；Aluminium powder, bronze, silver
The various metallic powdery pigments such as powder, copper powder, bronze powder, brass powder；Flaky pigment, the mica flake pigments of these metals；Covering
The metallic pigments, pearlescent pigment such as the mica flake pigments of the form of metal oxide, micaceous iron oxide pigment；Graphite, charcoal
It is black etc..
It as extender pigment, such as can enumerate: precipitability barium sulfate, whiting, winnofil, calcium bicarbonate, cool
Water stone, alumina white, silica, hydrated SiO 2 fine powder (white carbon black, white carbon), anhydride silica superfine powder
(aerosil), silica sand (Silica sand), talcum, precipitability magnesium carbonate, bentonite, clay, kaolin, loess etc..
In turn, it as plastic pigment, such as can enumerate: Dainippon Ink Chemicals's system " GRANDOLL PP-1000 ", " PP-
2000S " etc..
Pigment used in the present invention, from durability, weatherability, aesthetic appearance it is excellent from the aspect of, more preferably as
The inorganic oxides such as titanium oxide, the zinc white of white pigment, the carbon black as black pigment.
The mass ratio of pigment used in the present invention is total relative to polyisocyantates composition (X) and polyalcohol (Y)
The case where 100 mass parts are set as 1~400 mass parts, wherein 10~300 mass parts is counted, from the excellent side such as cementability, anticaking capacity
Face considers to be preferred.
In addition carbamate system bonding agent of the invention can also use adhesion promoters.Adhesion promoters can be enumerated
Out: the coupling agents, epoxy resin such as silane coupling agent, titanate esters system coupling agent, aluminium system.
It as silane coupling agent, such as can enumerate: γ aminopropyltriethoxy silane, gamma-amino propyl front three
Oxysilane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl)-gamma-amino propyl front three
The amino silanes such as base dimethoxysilane, N- phenyl-gamma-amino propyl trimethoxy silicane；β-(3,4- epoxycyclohexyl) second
Base trimethoxy silane, γ-glycidyl ether oxypropyltrimethoxysilane, three ethoxy of γ-glycydoxy
The epoxy silanes such as base silane；Vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltriethoxysilane, vinyl trimethoxy
The vinyl silanes such as base silane, γ-methacryloxypropyl trimethoxy silane；Hexamethyldisilazane, γ-sulfydryl third
Base trimethoxy silane etc..
It as titanate esters system coupling agent, such as can enumerate: tetraisopropoxy titanium, four titanium n-butoxides, butyl titanate
Dimer, four stearyl of metatitanic acid, acetyl acetone titanium, lactic acid titanium, four ethohexadiol titanate esters, four stearic oxygroup titaniums etc..
In addition, as aluminium system coupling agent, such as acetyl alkoxy aluminum-diisopropoxide can be enumerated etc..
As epoxy resin, usual commercially available table-dimorphism, phenolic varnish type, Beta-methyl table chlorine type, cyclic rings can be enumerated
Oxidative ethane type, glycidyl ether type, glycidyl ester type, polyglycols ether type, glycol ether type, epoxidized fatty acid ester type,
The various epoxy resin such as polybasic carboxylic acid ester type, aminoglycidyl type, resorcinol type.
If desired carbamate system bonding agent of the invention can also contain other additives in addition to the foregoing.As
Additive, such as can enumerate: levelling agent；The fine inorganic particles such as colloidal silicon dioxide, alumina sol；Polymethylacrylic acid
Organic fine grained of methyl esters system；Defoaming agent；Anti-sagging agent；Ricinate；Viscous regulator；Ultraviolet absorbing agent；Metal subtracts
Agent living；Peroxide decomposer；Fire retardant；Reinforcing agent；Plasticizer；Lubricant；Antirust agent；Fluorescent whitener；Inorganic system's heat
Light absorbers；Fireproof agent；Antistatic agent；Dehydrating agent etc..
These pigment, adhesion promoters, additive may be combined in any one in glycol composition and polyisocyanates
Ingredient in, or can be used as the 3rd ingredient and be compounded in coating and used.
By making the carbamate system bonding agent of the invention being described in detail above in common polyalcohol/isocyanates
Condition of cure under solidify and solidfied material of the invention can be obtained.
In addition, laminate film of the invention obtains in the following way: by the ammonia of the invention of detailed description above
Carbamate system bonding agent is coated on the first plastic film, and the second plastic film is then laminated on coated face, makes the bonding agent
Layer solidification.
Specifically, can be enumerated when carbamate system bonding agent of the invention is used as solvent type bonding agent
Following method: it is thin that carbamate system bonding agent of the invention with such as roll-coater coating method is coated on the first plastics
Film is bonded other substrates after being then dried under conditions of 60~90 DEG C.For coated conditions, common roll-coater
In the case where, preferably 500~2500mPas or so in the state of being heated to 25 DEG C~120 DEG C or so.
On the other hand, the case where no-solvent type, the following methods can be enumerated: by carbamate system bonding agent of the invention
To be for example coated on the first plastic film using roll-coater coating method, then it is bonded under the premise of without drying process
Other substrates.It is excellent in the state of being heated to 25 DEG C~120 DEG C or so the case where common roll-coater for coated conditions
Select 500~2500mPas or so.
In addition for coating weight, solvent type situation coating weight uses about 1.0~4.0g/m2It is advisable, the feelings of no-solvent type
Condition is with about 0.5~3.0g/m2Left and right use is advisable.The case where no-solvent type, has used carbamate system of the invention to be bonded
The case where agent, solidified bonding agent with 6~24 hours under room temperature or heating after laminating, showed practical physical property.
It as the first plastic film used herein, can enumerate: PET (polyethylene terephthalate) film, nylon
Basement membranes, the aluminium foils such as film, OPP (biaxial stretch-formed polypropylene) film, aluminium-vapour deposition film etc., in addition, as aforementioned other substrates, it can
Enumerate: CPP (tensionless winkler foundation polypropylene) film, LLDPE (straight-chain low density polyethylene) film etc. seal film.
As previously mentioned, in the present invention in order to have the adhesive property and durability/stability excellent for metal covering, first
Plastic film is particularly preferably aluminium foil or aluminium-vapour deposition film.
Thus obtained laminate film can be used for industry mainly as the packaging material of filling detergent, reagent.As tool
The purposes of body can be enumerated as detergent, reagent: washing washes agent, liquid detergent for kitchen use, bath liquid by liquid
Detergent, bath liquid soap, liquid shampoo, liquid hair conditioner etc..
For using packaging material manufactured by carbamate system bonding agent of the invention, filling detergent, reagent etc.
Content when needless to say, filling will not occur after a period of time layering etc. lamination constitute body removing, have
Excellent cementability, content patience.
Embodiment
The contents of the present invention and effect are illustrated in further detail by the following examples.In addition, described below
The raw polyol used in each embodiment and comparative example as raw material.Number shown in each embodiment, comparative example and synthesis example
Average molecular weight (Mn) is the value measured by the gel permeation chromatography (GPC) of following conditions.
Measurement device: TOSOH CORPORATION manufactures HLC-8220GPC
Column: TOSOH CORPORATION manufactures TSK-GUARDCOLUMN SuperHZ-L+TOSOH CORPORATION system
Make SuperHZM-M × 4 TSK-GEL
Detector: RI (differential refractometer)
Data processing: TOSOH CORPORATION manufactures Multi-Station GPC-8020modelII determination condition:
40 DEG C of column temperature
Solvents tetrahydrofurane
Flow velocity 0.35ml/ minutes
Standard: monodisperse polystyrene
Sample: the tetrahydrofuran solution for being calculated as 0.2 mass % with resin solid content conversion is carried out with microfilter
Filter resulting substance (100 μ l)
Embodiment 1 (manufacture of glycol composition (x1))
In the pet reaction container for having blender, thermometer, nitrogen ingress pipe, bead tube, moisture seperator etc., throw
Enter 198 mass parts of terephthalic acid (TPA), 162 mass parts of M-phthalic acid, 171 mass parts of adipic acid, 127 mass parts of ethylene glycol, two
0.14 mass parts of 159 mass parts of ethylene glycol and dibutyl tin dilaurate, in such a way that bead tube upper temp is no more than 100 DEG C
It is slowly heated and internal temperature is maintained at 250 DEG C.
Diformazan benzo is added when acid value is 2.5mgKOH/g makes refluxing xylene at 240 DEG C using moisture seperator,
Further sustained response to acid value is 1.5mgKOH/g or less.1333Pa is decompressed to hereinafter, being kept for 1.5 hours and removing diformazan
Benzene terminates esterification and obtains the polyester polyol that number-average molecular weight (Mn) is about 4000.
It is wherein being the ratio of 0.5 mass parts relative to 100 mass parts of foregoing polyester polyols in terms of solid component conversion
Styrene maleic anhydride copolymer (Cray Valley corporation " SMA 1000 ", phenylethylene/maleic anhydride=1/1 is added in example
Copolymer, molecular weight 5500SP value are 31.4 (J/cm3)1/2), and then solid component is adjusted to ethyl acetate dissolved dilution
75 mass % solution of concentration obtains glycol composition and (is abbreviated as " glycol composition (x1) " below.).
Embodiment 2 (manufacture of glycol composition (x2))
According to preparation method shown in embodiment 1 simultaneously using the same polyester polyol of identical Material synthesis, wherein with
Solid component conversion meter is to be added (the hydroxyl first of 2,2- bis- relative to the ratio that 100 mass parts of foregoing polyester polyols are 0.5 mass parts
Base) propionic acid (DMPA) [28.7 (J/cm of SP value3)1/2, acid value 414-418mgKOH/g], and then with ethyl acetate dissolved dilution and
It is adjusted to 75 mass % solution of solid component concentration, glycol composition is obtained and (is abbreviated as " glycol composition below
(x2)”。)。
Embodiment 3 (manufacture of glycol composition (x3))
According to preparation method shown in embodiment 1 simultaneously using the same polyester polyol of identical Material synthesis, wherein with
Solid component conversion meter is to be added (the hydroxyl first of 2,2- bis- relative to the ratio that 100 mass parts of foregoing polyester polyols are 0.5 mass parts
Base) butyric acid (DMBA) [27.4 (J/cm of SP value3)1/2, acid value 374-378mgKOH/g], and then with ethyl acetate dissolved dilution and
It is adjusted to 75 mass % solution of solid component concentration, glycol composition is obtained and (is abbreviated as " glycol composition below
(x3)”。)。
Embodiment 4 (manufacture of glycol composition (x4))
170 mass parts of toluene di-isocyanate(TDI) are added in the flask for having blender, thermometer, nitrogen ingress pipe, put down
Polypropylene glycol (Mitsui Chemicals, Inc.'s system " DIOL-700 ", bifunctional type's polypropylene glycol) 410 mass parts of average molecular weight 700 are put down
Polypropylene glycol (Mitsui Chemicals, Inc.'s system " DIOL-3000 ", the difunctionality of average molecular weight 3000 poly- the third two of average molecular weight 3000
Alcohol) 70 mass parts, which is heated to 95 DEG C, temperature is reduced to 70 DEG C after 1 hour and dipropyl is added wherein by stirring
25 mass parts of glycol, 2,2- bis- (methylol) propionic acid (DMPA) [28.7 (J/cm of SP value3)1/2, acid value 414-418mgKOH/g] 7
Mass parts are dissolved to as transparent.
In turn, temperature is reduced to 65 DEG C and 27 mass parts of diethanol amine (DEA) and dibutyl tin dilaurate is added
0.04 mass parts stir 1 hour and obtain the polyester polyols pure and mild 2 that number-average molecular weight (Mn) is about 4600,2- bis- (methylol)
The mixing of propionic acid (relative to aforementioned 100 mass parts of polyether urethane polyalcohol for 1 mass parts in terms of solid component conversion)
Object glycol composition (is abbreviated as " glycol composition (x4) " below.).
Synthesis example 1 (manufacture of polyalcohol (x5) (polyester urethane polyalcohol))
In the pet reaction container for having blender, thermometer, nitrogen ingress pipe, bead tube, moisture seperator etc., throw
Enter 123.5 mass parts of terephthalic acid (TPA), 123.5 mass parts of M-phthalic acid, 139.5 mass parts of adipic acid, 47 mass of dimeric dibasic acid
Part, 62 mass parts of ethylene glycol, 131 mass parts of neopentyl glycol, 59 mass parts of 1,6-HD and dibutyl tin dilaurate 0.12
Mass parts are slowly heated in such a way that bead tube upper temp is no more than 100 DEG C and internal temperature are maintained at 240 DEG C.
Diformazan benzo is added when acid value is 2.5mgKOH/g makes refluxing xylene at 230 DEG C using moisture seperator,
Further sustained response to acid value is 1.5mgKOH/g or less.1333Pa is decompressed to hereinafter, being kept for 1.5 hours and removing diformazan
Benzene terminates esterification and obtains the intermediate polyester polyol of acid value 0.5mgKOH/g.It is used into ethyl acetate dissolved dilution,
60 mass % solution of solid component concentration is made.In turn, relative to obtained 100 mass parts of intermediate polyester polyol, add
Enter 0.05 mass parts of 3 mass parts of isophorone diisocyanate and dibutyl tin dilaurate, is heated to 80 DEG C and carries out amino
The reaction of formic acid esterification until be created substantially absent free NCO base, obtain hydroxyl value 5 polyester urethane polyalcohol (with
It is lower to be abbreviated as " polyalcohol (x5) ".).The number-average molecular weight (Mn) of the polyester urethane polyalcohol is about 11000.
Synthesis example 2 (manufacture of polyalcohol (x6) (polyester urethane polyalcohol))
In the pet reaction container for having blender, thermometer, nitrogen ingress pipe, bead tube, moisture seperator etc., throw
It is pungent to enter 827 mass parts of M-phthalic acid, 725 mass parts of decanedioic acid, 154 mass parts of ethylene glycol, 720 mass parts of neopentyl glycol and two
0.15 mass parts of base tin dilaurate tin are slowly heated and by internal temperature in such a way that bead tube upper temp is no more than 100 DEG C
It is maintained at 260 DEG C.Diformazan benzo is added when acid value is 5mgKOH/g using moisture seperator returns at 250 DEG C dimethylbenzene
Stream further persistently carries out reaction until acid value is 2mgKOH/g or less.1333Pa is decompressed to hereinafter, being kept for 1.5 hours and being gone
Except dimethylbenzene, terminates esterification and obtain the intermediate polyester polyol of acid value 1mgKOH/g.It is dissolved with ethyl acetate
Dilution, is made 60 mass % solution of solid component concentration.In turn, relative to 100 parts of the obtained intermediate polyester polyol, add
Enter 0.025 mass parts of 4 mass parts of isophorone diisocyanate and dioctyl tin cinnamic acid tin, is heated to 80 DEG C and carries out amino
The reaction of formic acid esterification until be created substantially absent free NCO base, obtain hydroxyl value 7 polyester urethane polyalcohol (with
It is lower to be abbreviated as " polyalcohol (x6) ".).The number-average molecular weight (Mn) of the polyester urethane polyalcohol is about 9000.
(polyisocyantates composition (the y1) [polyisocyanates+change containing tetrabydrophthalic anhydride skeleton of embodiment 5
Close object (c3)] preparation)
The urea acid esters of isophorone diisocyanate is put into the flask for having blender, thermometer, nitrogen ingress pipe
Trimethylolpropane/adduct (the Mitsui Chemicals, Inc. of body (functional group number 3~4) 15 mass parts, xylylene diisocyanate
Make " TAKENATE D-110N ") 49 mass parts, 3a, 4,5,7a- tetrahydro -7- methyl -5- (tetrahydro -2,5- dioxo -3- furans
Base) the iso- benzofuran diketone of -1,3- [29.1 (J/cm of SP value3)1/2, acid value 849mgKOH/g] 3 mass parts, 33 mass of methyl ethyl ketone
Part, which is heated to 60 DEG C and stirs 1 hour and obtains polyisocyantates composition (polyisocyantates composition
(y1))。
(polyisocyantates composition (the y2) [polyisocyanates+change containing tetrabydrophthalic anhydride skeleton of embodiment 6
Close object (c3)] preparation)
In the flask for having blender, thermometer, nitrogen ingress pipe put into 30 mass parts of isophorone diisocyanate,
Trimethylolpropane/adduct (Mitsui Chemicals, Inc.'s system " TAKENATE D-100N ") 32 matter of xylylene diisocyanate
Measure part, 3a, 4,5,7a- tetrahydro -7- methyl -5- (tetrahydro -2,5- dioxo -3- furyl) iso- benzofuran diketone of -1,3-
[29.1 (J/cm of SP value3)1/2, acid value 849mgKOH/g] 1 mass parts, 37 mass parts of methyl ethyl ketone, which is heated to 60 DEG C
And it stirs 1 hour and obtains polyisocyantates composition (polyisocyantates composition (y2)).
Synthesis example 3 (manufacture of polyalcohol (x7) (polyester polyol))
In the pet reaction container for having blender, thermometer, nitrogen ingress pipe, bead tube, moisture seperator etc., throw
Enter 198 mass parts of terephthalic acid (TPA), 162 mass parts of M-phthalic acid, 171 mass parts of adipic acid, 127 mass parts of ethylene glycol, two
0.14 mass parts of 159 mass parts of ethylene glycol and dibutyl tin dilaurate, in such a way that bead tube upper temp is no more than 100 DEG C
It is slowly heated and internal temperature is maintained at 250 DEG C.Diformazan benzo is added when acid value is 2.5mgKOH/g to separate using moisture
Machine makes refluxing xylene at 240 DEG C, and further sustained response to acid value is 1.5mgKOH/g or less.Be decompressed to 1333Pa with
Under, dimethylbenzene is kept for 1.5 hours and removed, terminates esterification and obtains the polyester polyols that number-average molecular weight (Mn) is about 4000
Alcohol (is abbreviated as " polyalcohol (x7) " below.75 matter of solid component concentration is made with ethyl acetate dissolved dilution wherein
Measure % solution.
Comparative example 1 (manufacture of glycol composition (x8))
In the pet reaction container for having blender, thermometer, nitrogen ingress pipe, bead tube, moisture seperator etc., throw
Enter 198 mass parts of terephthalic acid (TPA), 162 mass parts of M-phthalic acid, 171 mass parts of adipic acid, 127 mass parts of ethylene glycol, two
0.14 mass parts of 159 mass parts of ethylene glycol and dibutyl tin dilaurate, in such a way that bead tube upper temp is no more than 100 DEG C
It is slowly heated and internal temperature is maintained at 250 DEG C.Diformazan benzo is added when acid value is 2.5mgKOH/g to separate using moisture
Machine makes refluxing xylene at 240 DEG C, and further sustained response to acid value is 1.5mgKOH/g or less.Be decompressed to 1333Pa with
Under, dimethylbenzene is kept for 1.5 hours and removed, terminates esterification and obtains the polyester polyol of number-average molecular weight about 6000.
Wherein by solid component conversion in terms of relative to 100 mass parts of foregoing polyester polyols be 5.3 mass parts ratio
Styrene maleic anhydride copolymer is added, and (Cray Valley corporation " SMA 1000 ", phenylethylene/maleic anhydride=1/1 are total
Polymers, molecular weight 5500SP value are 31.4 (J/cm3)1/2), and then it is dense with ethyl acetate dissolved dilution to be adjusted to solid component
75 mass % solution are spent, glycol composition is obtained and (is abbreviated as " glycol composition (x8) " below.).
Embodiment 7~14 and comparative example 2~3
According to table 1 or the composition of table 2, it is compounded host agent and curing agent, solid component concentration uses acetic acid as shown in table 1 or table 2
Ethyl ester is adjusted and is prepared for adhesive A~J.Then, having carried out following aluminium-vapour deposition disappearances prevents test and the layer of effect
Press ocular estimate test.
In table 1, table 2, " polyisocyanates (y3) " is relative to 1 mole of addition of trimethylolpropane toluene diisocynate
Adduct type polyisocyanates made of 3 moles of ester (ethyl acetate solution, 75 mass % of nonvolatile component), " polyisocyanates
(y4) " be methylene diisocyanate polypropylene glycol modified object (ethyl acetate solution, 75 mass % of nonvolatile component, 25 DEG C
When 1500~2500mPas of viscosity, 3.4 mass % of NCO containing ratio).
(preventing property of aluminium-vapour deposition disappearance is tested)
It is 3.0g/m with coating weight using test laminating machine (MUSASHINO Corporation system)2Mode be coated on
On OPP (biaxial stretch-formed polypropylene) film with transparent black and blue ink print, after being dried and removing solvent, with
The aluminium-vapour deposition surface layer pressure of VMPET (aluminium-vapour deposition PET), and then be 3.0g/m with coating weight2Mode and LLDPE film carry out layer
Pressure, has made laminate.
Then, curing in 40 DEG C × 3 days is carried out to the laminated film and makes bonding agent curing of coating, obtain OPP film/viscous
Connect this 3 layers of laminated films of agent/VMPET/ bonding agent/LLDPE film.Film, ink use substance below.
OPP film: 20 μm of Co. Ltd. system PYLEN FILM-OT P2161 spins in Japan
VMPET film: 12 μm of Co., Ltd.VM-PET1310 of TORAY ADVANCED FILM
LLDPE film: 60 μm of TUX-HC of Tohcello Co., Ltd.
Use ink:
(Lan Mo) DIC corporation " UNIVURE NT R507 ゲ Application シ ョ Network ア イ K1 "
(chalk) DIC corporation " the white K1 of XS-824 R794 "
Using after curing the laminated film production 120mm × 120mm size pouch, as content, be filled with
Mass ratio 1:1:1 is compounded with simulated foods 70g made of vinegar, salad oil, meat pulp juice.For the pouch of production, at 98 DEG C
It is lower carry out 60 minutes boil sterilization processing after, take care of 6 months, have rated by visual observation monochromatic and blue in 50 DEG C of insulating box
The appearance of black part.
Zero: appearance is unchanged
×: aluminium-vapour deposition disappears
(laminated appearance validation test)
Using the bonding agent prepared in each embodiment and comparative example, and by with aforementioned " aluminium-vapour deposition disappear preventing property test "
Used in the identical base film of substance and same coated amount, utilize DL-600DX dry laminating machine (Orient Sogyo
Co., Ltd.'s system) it was laminated with 250m/ minutes, obtain OPP film/bonding agent/this 3 layers of VMPET/ bonding agent/LLDPE film
Laminated film.It confirmed the appearance of the laminated film after being just laminated by visual observation.
Zero: indicating without entrainment bubble.
×: there is entrainment to steep.
[table 1]
[table 2]
Claims (17)
1. a kind of carbamate system bonding agent, which is characterized in that contain:
Selected from by polyester polyol (a1), polyester urethane polyalcohol (a2) and polyether urethane polyalcohol (a3) group
At group in polyalcohol (A),
Polyisocyanates (B) and
SP value is 20~32 (J/cm3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value,
To contain the carboxylated compound (C) relative to the ratio that 100 mass parts of polyalcohol (A) are 0.01~1.5 mass parts.
2. carbamate system bonding agent according to claim 1, wherein the carboxylated compound (C) is aromatic series
The copolymer of ethylene and maleic anhydride.
3. carbamate system bonding agent according to claim 1, wherein the carboxylated compound (C) is to contain hydroxyl
The aliphatic carboxylic acid of base.
4. carbamate system bonding agent according to claim 1, wherein the carboxylated compound (C) is that have four
The compound of hydrogen phthalic anhydride skeleton.
5. a kind of carbamate system bonding agent glycol composition, which is characterized in that contain: selected from by polyester polyol
(a1), the polyalcohol (A) in the group of polyester urethane polyalcohol (a2) and polyether urethane polyalcohol (a3) composition
And SP value is 20~32 (J/cm3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value, relative to polyalcohol
(A) 100 mass parts are that the ratio of 0.01~1.5 mass parts contains the carboxylated compound (C).
6. carbamate system bonding agent glycol composition according to claim 5, wherein in addition to the polyalcohol
(A) and except the carboxylated compound (C), so with solid component concentration be 60~80 mass % ratio contain it is organic molten
Agent (D).
7. carbamate system bonding agent glycol composition according to claim 5, wherein the carboxylated conjunction
Object (C) is the copolymer of aromatic vinyl and maleic anhydride.
8. carbamate system bonding agent glycol composition according to claim 5, wherein the carboxylated conjunction
Object (C) is the aliphatic carboxylic acid containing hydroxyl.
9. carbamate system bonding agent glycol composition according to claim 5, wherein the carboxylated conjunction
Object (C) is the compound with tetrabydrophthalic anhydride skeleton.
10. a kind of carbamate system bonding agent polyisocyantates composition, which is characterized in that contain: polyisocyanates (B)
It is 20~32 (J/cm with SP value3)1/2And the carboxylated compound (C) of 250~1000mgKOH/g of acid value.
11. carbamate system bonding agent polyisocyantates composition according to claim 10, wherein described to contain carboxylic
Based compound (C) is the copolymer of aromatic vinyl and maleic anhydride.
12. carbamate system bonding agent polyisocyantates composition according to claim 10, wherein described to contain carboxylic
Based compound (C) is the aliphatic carboxylic acid containing hydroxyl.
13. carbamate system bonding agent polyisocyantates composition according to claim 10, wherein described to contain carboxylic
Based compound (C) is the compound with tetrabydrophthalic anhydride skeleton.
14. carbamate system bonding agent according to claim 1, wherein the polyalcohol (A) and the polyisocyanic acid
The use ratio of ester (B) is the equivalent of the isocyanate group in the polyisocyanates (A) and the hydroxyl in the polyalcohol (B)
Than the ratio that [isocyanate group/hydroxyl] is 1.0~5.0.
15. a kind of solidfied material is to solidify carbamate system bonding agent according to any one of claims 1 to 4
's.
16. a kind of laminate film is to be coated on carbamate system bonding agent according to any one of claims 1 to 4
The second base film is then laminated in first base material film on coated face, made of solidifying the adhesive layer.
17. laminate film according to claim 16, wherein the first base material film is that metal foil or metal evaporation are thin
Film, and second base film is tensionless winkler foundation polypropylene film or low-density polyethylene film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016124577 | 2016-06-23 | ||
| JP2016-124577 | 2016-06-23 | ||
| PCT/JP2017/020421 WO2017221661A1 (en) | 2016-06-23 | 2017-06-01 | Urethane-based adhesive, polyol composition for urethane-based adhesive, polyisocyanate composition for urethane-based adhesive, hardened material of urethane-based adhesive, and lamination film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109462992A true CN109462992A (en) | 2019-03-12 |
| CN109462992B CN109462992B (en) | 2020-04-17 |
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|---|---|---|---|
| CN201780039001.9A Active CN109462992B (en) | 2016-06-23 | 2017-06-01 | Urethane adhesive, cured product and laminated film thereof, polyol for adhesive, and polyisocyanate composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6278166B1 (en) |
| CN (1) | CN109462992B (en) |
| WO (1) | WO2017221661A1 (en) |
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| CN115820195A (en) * | 2022-08-15 | 2023-03-21 | 杭州星华反光材料股份有限公司 | Polyurethane glue for high-brightness reflective material and application thereof |
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| JP6863524B2 (en) * | 2018-08-01 | 2021-04-21 | Dic株式会社 | Adhesive composition and surface protective film |
| JP7206888B2 (en) * | 2018-12-19 | 2023-01-18 | Dic株式会社 | Reactive adhesives, laminated films, and packages |
| JP7439391B2 (en) * | 2019-04-19 | 2024-02-28 | ａｒｔｉｅｎｃｅ株式会社 | Adhesive composition and manufacturing method thereof, laminated film and packaging body |
| JP7088138B2 (en) * | 2019-07-29 | 2022-06-21 | 凸版印刷株式会社 | Laminates and packaging bags |
| JP7231095B2 (en) * | 2019-07-29 | 2023-03-01 | 凸版印刷株式会社 | Laminates and packaging bags |
| JP7443763B2 (en) * | 2019-12-25 | 2024-03-06 | ａｒｔｉｅｎｃｅ株式会社 | Adhesive composition and laminate |
| WO2021246360A1 (en) * | 2020-06-02 | 2021-12-09 | 東洋インキＳｃホールディングス株式会社 | Two-pack type curable adhesive, multilayer body and package |
| TW202323471A (en) * | 2021-12-14 | 2023-06-16 | 日商Ｄｉｃ股份有限公司 | Adhesive, laminate, and packaging material |
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| JP4771276B2 (en) * | 2005-03-31 | 2011-09-14 | 日本ポリウレタン工業株式会社 | Laminating adhesive |
| JP6210306B2 (en) * | 2013-12-19 | 2017-10-11 | Dic株式会社 | Solvent-free two-component curable laminate adhesive composition |
| JP6617916B2 (en) * | 2015-11-19 | 2019-12-11 | Dic株式会社 | Polyol composition for solventless adhesive, solventless adhesive, and laminated film |
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2017
- 2017-06-01 WO PCT/JP2017/020421 patent/WO2017221661A1/en active Application Filing
- 2017-06-01 JP JP2017549817A patent/JP6278166B1/en active Active
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|---|---|---|---|---|
| CN1445261A (en) * | 2002-03-19 | 2003-10-01 | 罗姆和哈斯公司 | Carbamate polymer composition |
| CN1467259A (en) * | 2002-06-10 | 2004-01-14 | ��������ķ������ | Urethane polymer compositions |
| JP2005290285A (en) * | 2004-04-02 | 2005-10-20 | Toyo Ink Mfg Co Ltd | Adhesive for dry laminate for metal film |
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| JPWO2017221661A1 (en) | 2018-06-21 |
| WO2017221661A1 (en) | 2017-12-28 |
| CN109462992B (en) | 2020-04-17 |
| JP6278166B1 (en) | 2018-02-14 |
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