KR20020092704A - Polyisocyanate curing agent for laminate adhesive and its production - Google Patents

Abstract

PURPOSE: Provided are a polyisocyanate hardener for lamination adhesive, which can reduce an aging time without reducing a pot life, and has excellent adhesion, and a method for producing the same. CONSTITUTION: The polyisocyanate hardener comprises (A) isocyanate group terminated prepolymer having isocyanurate group and urethane group, obtained by reacting (a1) organic polyisocyanate at least comprising an aromatic diisocyanate and (a2) active hydrogen-containing compound at least comprising a diol compound having number average molecular weight of 100-2,000. The organic polyisocyanate is (a1) aromatic diisocyanate, and the hydrogen-containing compound is (a2) diol compound having number average molecular weight of 100-2,000.

Description

Polyisocyanate hardener for laminated adhesive and its manufacturing method {POLYISOCYANATE CURING AGENT FOR LAMINATE ADHESIVE AND ITS PRODUCTION}

The present invention relates to a polyisocyanate curing agent for laminated adhesive that can shorten aging time without shortening pot life and has good adhesiveness, and a method for producing the same.

In recent years, as a packaging method, flexible packaging is remarkable due to the strength of packaging, product protection, workability at packaging, propagation effect by packaging, and reduction of packaging cost due to cheap mass supply of film. Has been developing. As an adhesive used for the manufacture of such a film or a laminate of sheets, it is generally preferred to have a main ingredient having an active hydrogen group from the point of excellent adhesion performance, cold resistance, heat resistance, and a wide range of adaptation to substrates such as various plastics and metal foils. Two-component polyurethane adhesives made of a curing agent having an isocyanurate group have become mainstream.

Japanese Laid-Open Patent Publication No. 93-51574 discloses a polyester polyurethane polyol, a polyester resin mixture having a carboxyl group at the molecular end, an orthophosphoric acid or its ester compound, and an organic isocyanate compound, and a silane coupling agent if necessary. The adhesive composition which consists of is disclosed, and the meaning that the urethane modified body and isocyanurate modified body of tolylene diisocyanate can be used as an organic isocyanate compound is described.

In addition, Japanese Patent Application Laid-Open No. 88-110272 discloses one or two or more polyols among polyether polyols, polyester polyols, polyether urethane polyols, and polyester urethane polyols, isocyanate group-containing silane coupling agents, and polyisocyanate curing agents. An adhesive composition for composite lamination is disclosed.

However, although shortening of the hardening time of the adhesive agent in a lamination process is calculated | required, there are few conventional hardening | curing agents for laminated adhesives considering the reactivity with the subject matter. That is, since the hardening reaction of the adhesive agent after application | coating is very slow, the hardening promoting process called aging is needed. Specifically, it is necessary to fully cure the adhesive by storing the laminated processed film in an insulation chamber at 35 to 60 ° C. for about 3 to 5 days and aging. At this time, since the degree of curing of the adhesive is changed depending on the aging conditions, the adhesive strength of the laminated film may be affected. If the aging is insufficient, delamination due to poor curing of the adhesive may be caused. . In particular, aliphatic polyurethane adhesives require quite a long time for this curing reaction. Therefore, such an aging process is an indispensable process in the dry lamination process, making it difficult to cope with short-term delivery. In addition, there was a need for equipment investment for the installation of an insulation chamber for aging, and utilities for subsequent insulation. In addition, although the technique of Unexamined-Japanese-Patent No. 88-11027 has improved the adhesiveness, chemical resistance, and heat resistance of a laminated adhesive, it does not consider at all about the shortening of an aging time.

In order to shorten the aging time, the addition of a catalyst is generally effective. As such a technique, the technique of Unexamined-Japanese-Patent No. 97-316422 is mentioned. However, although the technique of Japanese Patent Laid-Open No. 97-316422 simply combines a catalyst with a polyurethane resin (solution), the aging time is shortened, but this time the pot life after mixing the main material and the curing agent (available time) A new problem that shortens to) occurs. Short pot life not only results in loss of the adhesive, but also often causes the adhesive to solidify, leading to failure of the application apparatus.

Japanese Patent Application Laid-Open No. 85-15419 discloses a polyisocyanate resin obtained by reacting an isocyanurate modified product of tolylene diisocyanate with a polyhydric alcohol having a number average molecular weight of 5,000 or less. Examples of the organic polyisocyanate as a curing agent described in Japanese Patent Application Laid-Open No. 93-51574 include a low molecular weight isocyanate compound, a polyurethane isocyanate obtained by reacting a low molecular weight isocyanate compound with water or a polyhydric alcohol, and a low molecular weight isocyanate compound. Dimers, trimers, etc. are mentioned.

However, Japanese Patent Application Laid-Open No. 85-15419 discloses that the polyisocyanate resin is useful as a curing agent for paint, but there is no description suggesting that the polyisocyanate resin be used as a curing agent for a laminated adhesive. In addition, Japanese Patent Laid-Open No. 93-51574 discloses no description suggesting an isocyanate group terminal prepolymer having a urethane group and an isocyanurate group obtained by reacting a diisocyanate with a polymer polyol. In the polyisocyanate curing agent disclosed in Japanese Patent Laid-Open No. 93-51574, it is difficult to solve the problem of shortening the aging time without shortening the pot life.

An object of the present invention is to provide a polyisocyanate curing agent for a laminated adhesive which can shorten the aging time without shortening the pot life and has good adhesiveness, and particularly can withstand high retort, and a manufacturing method thereof.

The present inventors earnestly examined and found that the said objective can be achieved by the polyisocyanate hardener obtained from a specific polyisocyanate and a specific polyol and having a specific group, and came to complete this invention.

That is, this invention is the following (1)-(10).

(A) (A) isocyanurate group obtained by making organic polyisocyanate containing (a1) aromatic diisocyanate at least, and (a2) the active hydrogen group containing compound containing at least the diol compound of the number average molecular weights 100-2,000. Isocyanate group terminal prepolymer which has a urethane group is contained, The polyisocyanate hardening | curing agent for laminated adhesives characterized by the above-mentioned.

(A) (A) isocyanurate group obtained by making organic polyisocyanate containing (a1) aromatic diisocyanate at least, and (a2) the active hydrogen group containing compound containing at least the diol compound of the number average molecular weights 100-2,000. An isocyanate group terminal prepolymer having a urethane group and (B) an isocyanate group terminal prepolymer having a urethane group are contained.

(3) (A) isocyanurate group obtained by making organic polyisocyanate containing (a1) aromatic diisocyanate at least, and (a2) the active hydrogen group containing compound containing at least the diol compound of the number average molecular weights 100-2,000. An isocyanate group terminal prepolymer having a urethane group, and (C) a silane coupling agent represented by the following general formula (1).

Formula 1

OCN- (CH ₂ ) _m -Si (OR) ₃

In the above formula, R means a methyl group or an ethyl group, m is an integer of 1-5.

(4) (A) isocyanurate group obtained by making organic polyisocyanate which contains (a1) aromatic diisocyanate at least, and (a2) the active hydrogen group containing compound containing at least the diol compound of the number average molecular weights 100-2,000. An isocyanate group terminal prepolymer having a urethane group, (B) an isocyanate group terminal prepolymer having a urethane group, and (C) a silane coupling agent represented by the following general formula (1).

Formula 1

OCN- (CH ₂ ) _m -Si (OR) ₃

In the above formula, R means a methyl group or an ethyl group, m is an integer of 1-5.

(5) As a manufacturing method of the polyisocyanate hardening | curing agent for laminated adhesives of (1),

(i) urethane-forming an organic polyisocyanate containing at least (a1) aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to produce a urethane-modified polyisocyanate. fair; And

(ii) isocyanurating the urethane-modified polyisocyanate to produce an isocyanate group-end prepolymer having an isocyanurate group and a urethane group. .

(6) As a method for producing a polyisocyanate curing agent for laminated adhesive of (1),

(iii) isocyanurating an organic polyisocyanate containing at least aromatic diisocyanate to produce isocyanurate-modified polyisocyanate; And

(iv) urethane-forming the isocyanurate-modified polyisocyanate and (a2) an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000, thereby (A) an isocyanate having an isocyanurate group and a urethane group A method for producing a polyisocyanate curing agent for a laminated adhesive, comprising the step of producing a terminal terminal prepolymer.

(7) As a manufacturing method of the polyisocyanate hardening | curing agent for laminated adhesives of (1),

(v) urethanization reaction and isocyanurate reaction simultaneously with an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) And (A) a step of producing an isocyanate group terminal prepolymer having an isocyanurate group and a urethane group.

(8) As a manufacturing method of the polyisocyanate hardening | curing agent for laminated adhesives of (2),

(i) urethane-forming an organic polyisocyanate containing at least (a1) aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to produce a urethane-modified polyisocyanate. fair;

(ii) isocyanurating the urethane-modified polyisocyanate to produce (A) an isocyanate group-end prepolymer having an isocyanurate group and a urethane group; And

(vi) A method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group. .

(9) As a manufacturing method of the polyisocyanate hardening | curing agent for laminated adhesives of (2),

(iii) isocyanurating an organic polyisocyanate containing at least aromatic diisocyanate to produce isocyanurate-modified polyisocyanate;

(iv) urethaneization of the isocyanurate-modified polyisocyanate and (a2) an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to (A) an isocyanate having an isocyanurate group and a urethane group Preparing a group terminal prepolymer; And

(vii) a method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group .

(10) As a manufacturing method of the polyisocyanate hardening | curing agent for laminated adhesives of (2),

(v) urethanization reaction and isocyanurate reaction simultaneously with an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) (A) producing an isocyanate group terminal prepolymer having an isocyanurate group and a urethane group; And

(viii) A method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group. .

Embodiment of the invention

Hereinafter, the present invention will be described in detail.

First, the raw material used for this invention is demonstrated.

The isocyanate group terminal prepolymer (A) which has isocyanurate group and urethane group in this invention contains the organic polyisocyanate containing (a1) aromatic diisocyanate at least and (a2) the diol compound of the number average molecular weights 100-2,000. The active hydrogen group-containing compound is obtained by urethane-forming and isocyanurate-reacting an excessive amount of isocyanate groups with respect to the active hydrogen group.

Examples of the (a1) aromatic diisocyanate include 2,4-tolylene diisocyanate (hereinafter abbreviated as 2,4-TDI), 2,6-tolylene diisocyanate (hereinafter abbreviated as 2,6-TDI) and xylene-1 , 4-diisocyanate (hereinafter abbreviated 1,4-XDI), xylene-1,3-diisocyanate (hereinafter abbreviated 1,3-XDI), 4,4'-diphenylmethane diisocyanate (hereinafter MDI) Abbreviated), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'-di Isocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediisocyanate, m- Phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, these Ooh Retan modified bodies (except polyols used for urethane modification except for (a2) diol compounds having a number average molecular weight of 100 to 2,000 to be described later), urea modified bodies, biuret modified substances, uretdione modified substances, isocyanurate A modified body, a uretdione isocyanurate modified body, a carbodiimide modified body, and a uretonimine modified body can be mentioned. These are used alone or as a mixture of two or more kinds.

Preferred (a1) aromatic diisocyanates in the present invention are 2,4-TDI and / or 2,6-TDI, in particular 2,4-TDI, in consideration of reactivity with the subject matter, productivity of the curing agent, adhesiveness and the like.

In this invention, organic polyisocyanate other than (a1) can be used together as needed, For example, aromatic polyisocyanate, such as polyphenylene polymethylene polyisocyanate and crude TDI, tetramethylene diisocyanate, hexamethylene diisocyanate (henceforth HDI) ), Aliphatic diisocyanates such as decamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), hydrogenated TDI, hydrogenated xylylene diisocyanate (hereinafter abbreviated as H ₆ XDI) And diisocyanates such as cycloaliphatic diisocyanates such as hydrogenated diphenylmethane diisocyanate and tetramethyl xylene diisocyanate, urethane modified substances, urea modified substances, biuret modified substances, uretdione modified substances and isocyanurate modified compounds. Sieve, uretdione isocyanurate modified body, carbo Already it can be a de-modified product, urea modified product immigration tons.

The diol compound (a2) is a compound having substantially two hydroxyl groups in one molecule, having a number average molecular weight of 100 to 2,000, particularly preferably 500 to 1,800.

When the number average molecular weight of the (a2) diol compound is less than the said lower limit, the adhesiveness of an adhesive agent will fall easily. Moreover, when it exceeds the said upper limit, adhesion time will become long.

In addition, "having two substantially hydroxyl groups" means having two hydroxyl groups in one molecule. For example, in the case of polyester diol, although a part of the terminal is exactly carboxyl group, a carboxyl group usually becomes about 1% or less of the number-of-moles of a hydroxyl group, and it does not interfere substantially even if it is a complete diol compound.

(a2) When the hydroxyl group which a diol compound has substantially exceeds 2, it may gelatinize during manufacture of a polyisocyanate hardening | curing agent. In the case of less than two, the physical property of a laminated adhesive may fall.

Examples of such diol compounds include polyester diols, polyesteramide diols, polyether diols, polyester ether diols, polycarbonate diols, polycarbonate ester diols, polycarbonate ether diols, and polyolefin diols. These can be used individually or in mixture of 2 or more types.

As polyesterdiol and polyesteramide diol, for example, known succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalene 1 or more types of dicarboxylic acid, such as dicarboxylic acid, acid ester, or anhydride, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexane Diol, neopentylglycol, 1,8-octanediol, 1,9-nonanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol , 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-ecoic acid-1, 2-ethylene glycol, 2-n-octacoic acid-1,2-ethylene glycol, diethylene glycol , Low molecular diols such as dipropylene glycol, 1,4-cyclohexanedimethanol, alkylene oxide adducts of bisphenol A, hydrogenated bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, hexamethylenediamine, xylylene Dehydration condensation reaction with at least one of low molecular weight amino alcohols such as diamine and isophorone diamine, monoethanolamine, and N-methylethanolamine (however, the sum of hydroxyl groups and amino groups in one molecule is 2) What is obtained is mentioned. Furthermore, the lactone-type polyester diol etc. which are obtained by ring-opening-polymerization of cyclic ester (lactone) monomers, such as (epsilon) -caprolactone and (gamma) -valerolactone, can be mentioned using a low molecular diol, a low molecular diamine, or a low molecular amino alcohol as an initiator.

Examples of the polycarbonate diols and polycarbonate ester diols include low molecular diols used in the above-described polyester diols or their synthesis, and low molecules having one carbonate group in a molecule such as diethylene carbonate, dimethyl carbonate, diethyl carbonate and diphenyl carbonate. The thing obtained by a dealcohol reaction with a compound, a dephenol reaction, etc. are mentioned.

Examples of the polyetherdiol include poly (oxyethylene) diol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc., using, for example, low molecular diols, low molecular diamines or low molecular amino alcohols used in the synthesis of the above-described polyester diols; Poly (oxypropylene) diol, poly (oxytetramethylene) diol and the like, and polyetherdiol copolymerized therewith, and polyesteretherdiol and polycarbonateetherdiol prepared by using the above-described polyesterdiol and polycarbonatediol as initiators Can be mentioned.

Examples of the polyolefin diol include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, chlorinated polypropylene and chlorinated polyethylene having substantially two hydroxyl groups in one molecule.

Moreover, the above-mentioned low molecular diol used for the synthesis | combination of polyesterdiol is mentioned as a diol compound (a2), for example.

Preferred (a2) diol compounds in the present invention are those having side chain alkyl groups in consideration of adhesion and the like. As such a diol compound, for example, a dealcoholization reaction with a low molecular diol having a side chain and a polyester diol obtained from a dicarboxylic acid, a low molecular diol having a side chain with a diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like, and a dephenol reaction The polyether diol which added the alkylene oxide containing a C3 or more alkylene oxide to the obtained polycarbonate diol and bifunctional active-hydrogen group containing compound is mentioned. Particularly preferred diol compounds are polyesterdiols obtained from 3-methyl-1,5-pentanediol and adipic acid and poly (oxypropylene) diols.

In addition, in order to improve adhesiveness, improve compatibility with the subject, and the like, if necessary (a2) in addition to active hydrogen group-containing compounds other than diol compounds having a number average molecular weight of 100 to 2,000, such as low molecular diamines and low molecular amino alcohols described above, Low molecular polyols such as glycerin, trimethylolpropane (hereinafter abbreviated as TMP), pentaerythritol, polyols prepared from these materials, high molecular weight polyols having a number average molecular weight of more than 2,000, and low molecular monools such as polyethermonol can do.

The isocyanurate group content of the isocyanate group terminal prepolymer having the isocyanurate group and the urethane group (A) is preferably 5 to 25% by weight, more preferably 6 to 23% by weight in terms of solid content. When the isocyanurate group content is too small, the curing speed of the adhesive becomes slow, and further, the aging time tends to be long. Moreover, when there are too many, the viscosity of a polyisocyanate hardening | curing agent becomes large and workability tends to fall.

Moreover, in the isocyanate group terminal prepolymer (A) which has an isocyanurate group and a urethane group, 10-90 weight% is preferable in conversion of solid content, and, as for content of a diol compound, 15-85 weight% is more preferable. When content of (a2) is out of this range, adhesive strength will fall easily.

(A) 3-15 weight% is preferable in conversion of solid content, and, as for the isocyanate group content of the isocyanate group terminal prepolymer which has an isocyanurate group and a urethane group, 3-10 weight% is more preferable. When the isocyanate group content is too small, the adhesive strength tends to be insufficient. When content of an isocyanate group is too big | large, the softness | flexibility of a hardening adhesive agent falls or the hardening rate of an adhesive agent tends to become slow.

It is preferable that the isocyanate group terminal prepolymer which has (B) urethane group used for this invention is obtained by the urethanation reaction of (b1) organic diisocyanate and (b2) polyhydric alcohol. In addition, (B) does not have an isocyanurate group.

(bl) As organic diisocyanate, for example, aliphatic diisocyanates, alicyclic diisocyanates, urea modifications thereof, biuret modifications, carbodiimide modifications, and uretonimide modifications other than the above-mentioned (a1) aromatic diisocyanates Can be mentioned. Preferred (bl) organic diisocyanates in the present invention are aromatic diisocyanates, especially TDI, in view of their reactivity.

(b2) As the polyhydric alcohol, for example, low-molecular polyols such as glycerin, TMP, pentaerythritol, polyester polyols, polycarbonate polyols, polyether polyols prepared as raw materials, in addition to the diol compounds (a2) mentioned above Can be. Preferred (b2) polyhydric alcohols in the present invention are those having 2 to 5 hydroxyl groups substantially in consideration of crosslinking efficiency and the like, and having a molecular weight of 62 to 300.

(B) 5-30 weight% is preferable in conversion of solid content, and, as for the isocyanate group content of the isocyanate group terminal prepolymer which has a urethane group, 7-25 weight% is more preferable. When the isocyanate group content is too small, the adhesive strength tends to be insufficient. When an isocyanate group content is too big | large, the softness at the time of hardening of an adhesive agent tends to fall.

Moreover, as an isocyanate group terminal prepolymer which has (B) urethane group, what is shown below is mentioned specifically ,.

Polyisocyanates with urethane-modified TDI with TMP:

Coronate (registered trademark) L made by Nippon Polyurethane Industry

Sumi Joule (registered trademark) L-75 made of Sumitomo Bayer urethane

Takenate (registered trademark) D-102 made by Takeda Pharmaceutical Co., Ltd.

Polyisocyanates modified urethane with HDI by TMP:

Coronate HL made by Nippon Polyurethane Industry

Sumjul HT made of Tumi Sumitomo Bayer urethane

Takenate D-160N made by Takeda Pharmaceutical Co., Ltd.

Polyisocyanates with urethane-modified IPDI to TMP:

Takenate D-140N made by Takeda Pharmaceutical Co., Ltd.

Mytech (registered trademark) NY215A made by Mitsubishi Chemical

Polyisocyanates where urethane-modified XDI with TMP:

Takenate D-11ON made by Takeda Pharmaceutical Co., Ltd.

Polyisocyanates modified urethane with H ₆ XDI:

Takenate D-120N made by Takeda Pharmaceutical Co., Ltd.

The mixing ratio of the isocyanate group terminal prepolymer having (A) isocyanurate group and urethane group and (B) isocyanate group terminal prepolymer having urethane group in the polyisocyanate curing agent for laminated adhesive of the present invention is (A) / (B) = 100/0 to 100/100 is preferable, and (A) / (B) = 100/5 to 100/100 is particularly preferable. If there is too much (B), an aging time may become long.

5-20 weight% is preferable in conversion of solid content, and, as for the isocyanate group content of the polyisocyanate hardening | curing agent for laminated adhesive containing (A) and (B) of this invention, 7-18 weight% is more preferable.

The (C) silane coupling agent used for this invention is represented by following General formula (1).

Formula 1

OCN- (CH ₂ ) _m -Si (OR) ₃

In the above formula, R means a methyl group or an ethyl group, m is an integer of 1-5.

It is well known that the adhesiveness, heat resistance, chemical resistance, etc. of an adhesive agent are improved by using a silane coupling agent. However, when a silane coupling agent is previously mix | blended with the main body, especially the main body which has functional groups, such as an amino group and an epoxy group, coloring and thickening may arise with time. This is considered to be because the functional group in the subject and the alkoxysilyl group of the silane coupling agent react. In addition, since a silane coupling agent usually has functional groups, such as an amino group and an epoxy group, when a polyisocyanate hardening | curing agent and a silane coupling agent are mix | blended, the isocyanate group in a hardening | curing agent and the functional group in a silane coupling agent will react similarly with time, May cause thickening.

Therefore, in order to stabilize the laminated adhesive over time, it may store for every component and mix | blends each component just before use. However, a lot of hands went to a storage place and mix | blending of each component, and the two-component type laminated adhesive was desired. Moreover, if a silane coupling agent is not used, of course it becomes a two-component system, but in order to obtain the laminated | multilayer film for high retort, adhesiveness is lacking. For this reason, a silane coupling agent is needed for the laminated adhesive for high retort.

Since the functional groups of the (C) silane coupling agent used in the present invention are -NCO and -Si- (OR) ₃ (wherein R is a methyl group or an ethyl group), reacting with an isocyanate group terminal prepolymer under ordinary storage conditions none. For this reason, the polyisocyanate hardener of this invention has favorable stability with time.

In this invention, it is preferable that the addition amount of (C) silane coupling agent is 10 weight% or less with respect to the whole isocyanate group terminal prepolymer, and 0.1-8 weight% is especially preferable. When there is too much addition amount of (C), adhesiveness may fall and workability at the time of lamination | stacking adhesion may fall.

Various additives can also be mix | blended with the polyisocyanate hardening | curing agent for laminated adhesives of this invention as needed. Examples of the additive include pigments, dyes, solvents, thixotropic agents, antioxidants, ultraviolet absorbers, antifoaming agents, thickeners, dispersants, surfactants, mold inhibitors, antibacterial agents, preservatives, catalysts and fillers. There is no restriction | limiting in particular in a compounding method, A well-known method is used.

Next, each process in the manufacturing method of the polyisocyanate hardening | curing agent of this invention is described.

(I) The urethanation reaction process in this invention reacts the organic polyisocyanate containing at least (a1) aromatic diisocyanate, and the active hydrogen group containing compound containing at least the diol compound of (a2) number average molecular weights 100-2,000. It is a process to make it. At this time, although a well-known urethanation catalyst can be used, reaction does not proceed in particular in this invention. This is because the isocyanate group is present in excess of the active hydrogen group in the urethane-forming reaction, and since the isocyanate group is directly bonded to the aromatic ring, the reactivity is high. Moreover, the reaction temperature of urethanation is 0-120 degreeC, especially 20-100 degreeC is preferable.

(ii) The isocyanurate reaction process is carried out by adding an isocyanurate catalyst to the urethane-modified polyisocyanate obtained in (i).

Examples of the isocyanurate catalyst include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, tetramethylammonium acetate, tetraethylammonium acetate and tetrabutylammonium. Trialkyl hydroxy such as organic weak acid salts such as acetate, trimethyl hydroxypropylammonium hydroxide, trimethyl hydroxyethylammonium hydroxide, triethyl hydroxypropylammonium hydroxide and triethyl hydroxyethylammonium hydroxide Alkyl ammonium hydroxide, trimethyl hydroxypropylammonium acetate, trimethyl hydroxyethylammonium acetate, triethyl hydroxypropylammonium acetate, triethyl hydroxyethylammonium acetate, etc. Organic weak acid salt, triethylamine, triethylenediamine, 1,5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7,2,4,6 All well-known things, such as metal salts of alkyl carboxylic acids, such as tertiary amine, such as a tris (dimethylaminomethyl) phenol, an acetic acid, a caproic acid, a capric acid, an octylic acid, a myristic acid, and a naphthenic acid, can be used.

The addition amount of the isocyanurate catalyst is preferably in the range of 10 to 10,00 ppm in the reaction system. As addition method of this catalyst, divided addition is mentioned besides batch injection. In the case of split addition, each dose of catalyst may be the same or different. Moreover, as for the reaction temperature of isocyanurate reaction, 0-120 degreeC, especially 20-100 degreeC are preferable.

Where the isocyanate group content reaches the target value, the isocyanurate reaction terminator is added to stop the reaction. As this terminator, known acids such as inorganic acids such as phosphoric acid and hydrochloric acid, sulfonic acid groups, sulfamic acid groups and the like, and esters thereof and acyl halides thereof can be used.

The addition amount of the isocyanuration reaction terminator is preferably 0.5 to 2 moles, more preferably 0.8 to 1.8 moles with respect to the iso-anurate catalyst. When the addition amount of this stopper is too small, the isocyanurate reaction does not stop and there exists a possibility of causing the fall of the isocyanate group content of the polyisocyanate hardening | curing agent of this invention, and gelatinization. In addition, when there are too many, the polyisocyanate hardening | curing agent of this invention may cause cloudiness and a fall of adhesive strength.

The (iii) isocyanurate reaction step in the method of the present invention is carried out by adding an isocyanurate catalyst to an organic polyisocyanate containing at least (a1) aromatic diisocyanate.

The kind and addition amount of an isocyanurate catalyst, the addition time, addition amount, etc. of an isocyanurate reaction stopper are the same as that of (ii) mentioned above.

(iv) The urethanation reaction process is a process of carrying out a urethanation reaction of the isocyanurate modified polyisocyanate obtained by (iii) and the active hydrogen group containing compound containing at least the diol compound of (a2) number average molecular weights 100-2,000.

Although this urethanation reaction can use a well-known urethanization catalyst, it does not need to use it especially in this invention.

In the step (v) of the present invention, after (a1) an organic polyisocyanate containing at least an aromatic diisocyanate and (a2) an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 are added thereto, It is a process of adding and isocyanurizing a catalyst and making it react. As mentioned above, since this process advances even if a urethanation catalyst does not exist in particular, an isocyanuration reaction and a urethanation reaction take place simultaneously.

The kind and the addition amount of the isocyanurate catalyst, the addition time and the addition amount of the terminator, and the like are the same as in (ii) described above.

In each of the above production methods of the present invention, the molar ratio of the organic polyisocyanate containing at least (a1) aromatic diisocyanate and the active hydrogen group-containing compound containing at least the (a2) diol compound is an organic polyisocyanate / active hydrogen group. Containing compound = 2/1-100/1, It is preferable that it is 3/1-50/1 especially. When there are too many active hydrogen group containing compounds, the viscosity of a hardening | curing agent tends to become large too much. Moreover, when there are too few active hydrogen group containing compounds, the adhesiveness of an adhesive agent will fall easily.

The (vi) mixing step in the method of the present invention is an isocyanate group terminal prepolymer having (A) isocyanurate group and urethane group obtained through step (i) and (ii), and isocyanate group terminal having (B) urethane group It is a process of mixing a prepolymer. Although there is no restriction | limiting in particular in mixing conditions, When the mixing temperature is 30-80 degreeC, since the viscosity of a mixing system becomes low and mixing efficiency becomes high, it is preferable.

Process (vii) and process (viii) can be carried out as described in (vi) above.

Moreover, in each said manufacturing method of this invention, it is preferable to perform isocyanurate reaction using the organic solvent. This is because in the isocyanurate reaction, the reaction product becomes three-dimensional and difficult to dissolve in the solvent.

What is necessary is just to be inert in an isocyanate group as this organic solvent, For example, aromatic hydrocarbon solvents, such as toluene and xylene, ester solvents, such as ethyl acetate and butyl acetate, ketone solvents, such as methyl ethyl ketone and cyclohexanone, and ethylene glycol ethyl ether Glycol ether ester solvents such as acetate, propylene glycol methyl ether acetate, ethyl-3-ethoxy propionate, ether solvents such as tetrahydrofuran and dioxane, dimethylformamide, dimethylacetamide, and N-methylpyrroli Single or 2 or more types of aprotic polar solvents, such as a ton and furfural, are mentioned. In addition, the solid content is preferably carried out in the range of 10 to 90% by weight, more preferably 20 to 80% by weight. When solid content is too low, reaction time will become long. When the solid content is too high, the reaction product tends to be solidified and the workability is lowered. In the present invention, it is preferable to use an ester solvent, particularly an acetate ester solvent, in which residual solvent is reduced after lamination.

It is preferable that content of the free (unreacted) aromatic diisocyanate in the polyisocyanate hardener obtained in this way is 1 weight% or less. When there is too much content of free aromatic diisocyanate, working environment may fall because of bad smell.

In any of the above steps, the above-described various additives may be blended after or before the reaction. There is no restriction | limiting in particular in the mixing method, A well-known method is used.

(C) The silane coupling agent (A) the isocyanate group terminal prepolymer which has the urethane group (A) isocyanurate group obtained as mentioned above as needed, or (A) the isocyanate group terminal prepolymer which has an isocyanurate group and urethane group, and (B ) It is mixed with the isocyanate group terminal prepolymer which has a urethane group, and the polyisocyanate hardening | curing agent for laminated adhesive of the objective can be obtained.

The polyisocyanate hardener of this invention is mix | blended with the active-hydrogen group containing resin used as a subject, and then apply | coated to a to-be-adhered body, and is used for adhesion | attachment. The resin used in this subject is not particularly limited as long as it has a resin having an active hydrogen group, specifically, an alkyd resin and an acrylic resin modified with a polyurethane resin, a polyamide resin, a saturated or unsaturated polyester resin, a saturated fatty acid or an unsaturated fatty acid. , Fluororesin, epoxy resin, cellulose resin and the like. Preferred main resin is a polyurethane resin having good adhesion between different kinds of adherends and excellent durability.

More specifically, such a polyurethane resin is preferably a polyester-based polyurethane resin dissolved in an organic solvent. In addition, the polyurethane resin has a number average molecular weight of 1,000 to 100,000, a solid content of 5 to 80% by weight, and a viscosity of 10,000 mPa at 25 ° C. in consideration of the ease of application at the time of lamination and the adhesive strength. It is preferable that it is less than s.

It is preferable that the compounding ratio of a main body and a hardening | curing agent becomes a range which becomes active hydrogen group / isocyanate group = 9: 1-1: 9 in conversion of the molar ratio of the active hydrogen group and isocyanate group in a system.

As a coating apparatus of the adhesive agent which mix | blended the polyisocyanate hardening | curing agent of this invention, well-known things, such as an airless sprayer, an air sprayer, immersion, a roll applicator, a brush, are mentioned.

As for the bonding conditions of the adhesive agent which mix | blended the polyisocyanate hardening | curing agent of this invention, 0.1-1 Mpa is preferable at 10-180 degreeC, and 0.2-0.8 Mpa is especially preferable at 20-150 degreeC.

There is no restriction | limiting in particular in the film used in manufacture of laminated | multilayer film using the adhesive agent which mix | blended the polyisocyanate hardening agent of this invention, Polyolefin films, such as polyethylene terephthalate, Polyolefin films, such as polyethylene and a polypropylene, Poly, such as nylon Metal foil, such as an amide type film, aluminum foil and copper foil, an ethylene-vinyl acetate copolymer, and its saponification, cellophane, polyvinyl chloride, polyvinylidene chloride, polystyrene, paper, etc. are mentioned. Furthermore, those which have been subjected to such stretching treatment or surface treatments such as corona discharge treatment and various coating treatments can be suitably used.

Moreover, the adhesive agent which mix | blended the polyisocyanate hardening | curing agent of this invention can be used suitably as an adhesive agent not only between two layers of films but also between three layers or more multilayer films.

As for the aging conditions after lamination | stacking of the adhesive agent which mix | blended the polyisocyanate hardening agent of this invention, 5 hours or more are preferable at 20-70 degreeC, especially 10 hours or more at 25-50 degreeC. Moreover, 48 hours or more were required for the aging in the conventionally well-known laminated adhesive at the same temperature.

Example

Although an Example and a comparative example demonstrate this invention further in detail, this invention is limited at all by these and should not be interpreted. In addition, in an Example and a comparative example, "%" means "weight%."

[Production of isocyanate group terminal prepolymer having isocyanurate group and urethane group]

The symbol of the raw material used by the synthesis examples 1-11 is as follows.

TDI (1): 2,4-TDI

TDI (2): mixture of 2,4-TDI / 2,6-TDI = 80/20 (weight ratio)

Polyol A: Polyetherdiol which added the propylene oxide to 1,2-propanediol, and number average molecular weight = 500

Polyol B: polyetherdiol obtained by adding propylene oxide to 1,2-propanediol, number average molecular weight = 1,000

Polyol C: Polyetherdiol which added the propylene oxide to 1,2-propanediol, and number average molecular weight = 1,500

Polyol D: polyesterdiol obtained from 3-methyl-1,5-pentanediol and adipic acid, number average molecular weight = 1,000

Polyol E: polyesterdiol obtained from 3-methyl-1,5-pentanediol and adipic acid, number average molecular weight = 3,000

Monool A: polyether monool which added ethylene oxide to methanol, number average molecular weight = 400

Synthesis Example 1

After replacing the inside of the 1 L reactor equipped with a stirrer, a thermometer, a nitrogen sealing tube, and a cooler with nitrogen, 100 g of TDI (1) and 140 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. Infrared absorption (IR) analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 9.2%, and therefore the isocyanurate group content was 10.7%.

Subsequently, 37.8 g of polyol A was further added therein and reacted at 75 degreeC for 3 hours, and the isocyanate group terminal prepolymer NCO-A1 was obtained. IR analysis of NCO-A1 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-A1 was 5.7%, and therefore the isocyanurate group content was 9.3%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from gel permeation chromatography (GPC) analysis was 0.2%.

Synthesis Example 2

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 175 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. IR analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 7.6%, and therefore the isocyanurate group content was 9.9%.

Subsequently, 73.9g of polyol B was further added in this, and it reacted at 75 degreeC for 3 hours, and obtained the isocyanate group terminal prepolymer NCO-A2. IR analysis of NCO-A2 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-A2 was 4.2%, and therefore the isocyanurate group content was 7.8%. Solid content was 49.9%. In addition, the content of TDI (1) liberated from GPC analysis was 0.3%.

Synthesis Example 3

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 214 g of ethyl acetate were added and stirred uniformly. 113.5g of polyol C was thrown in this, and it was made to react at 75 degreeC for 3 hours. IR analysis confirmed the presence of isocyanate groups and urethane groups in the reaction product, but not hydroxyl groups. The isocyanate group content of this reaction product was 9.8%.

Subsequently, 0.5 g of magnesium naphthenate was further added therein, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction, thereby obtaining an isocyanate group terminal prepolymer NCO-A3. IR analysis of NCO-A3 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-A3 was 3.7%, and therefore the isocyanurate group content was 6.1%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from GPC analysis was 0.3%.

Synthesis Example 4

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 176 g of ethyl acetate were added and stirred uniformly. Into this, 73.9 g of polyol D and 0.5 g of magnesium naphthenate were added and subjected to isocyanurate reaction and urethane reaction at 75 ° C for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction, thereby obtaining an isocyanate group terminal prepolymer NCO-A4. IR analysis of NCO-A4 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-A4 was 4.2%, and therefore the isocyanurate group content was 7.8%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from GPC analysis was 0.4%.

Synthesis Example 5

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 172 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. IR analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 7.6%, and therefore the isocyanurate group content was 10.1%.

Subsequently, 61.6 g of polyol B and 10.0 g of monool A were added thereto, and the mixture was reacted at 75 ° C for 3 hours to obtain an isocyanate group terminal prepolymer NCO-A5. IR analysis of NCO-A5 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-A5 was 4.2%, and therefore the isocyanurate group content was 8.0%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from GPC analysis was 0.3%.

Synthesis Example 6

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (2) and 176 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. IR analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 7.5%, and therefore the isocyanurate group content was 9.8%.

Subsequently, 73.9 g of polyol B was further added thereto and reacted at 75 ° C. for 3 hours to obtain an isocyanate group terminal prepolymer NCO-A6. IR analysis of NCO-A6 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but no hydroxyl group. The isocyanate group content of NCO-A6 was 4.2%, and therefore the isocyanurate group content was 7.8%. Solid content was 50.0%. In addition, the content of TDI (2) liberated from the GPC analysis was 0.4%.

Synthesis Example 7

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 199 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. IR analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 8.0%, and therefore the isocyanurate group content was 8.2%.

Subsequently, 98.8g of polyol B was further added in this, and it reacted at 75 degreeC for 3 hours, and obtained the isocyanate group terminal prepolymer NCO-A7. IR analysis of NCO-A7 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but no hydroxyl group. The isocyanate group content of NCO-A7 was 3.9%, and therefore the isocyanurate group content was 6.1%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from the GPC analysis was 0.2%.

Synthesis Example 8

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 106 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. IR analysis confirmed the presence of isocyanate groups and isocyanurate groups in the reaction product. The isocyanate group content of this reaction product was 10.7%, and therefore the isocyanurate group content was 12.7%.

Subsequently, 5.8 g of 1,2-propylene glycol was further added in this, and it reacted at 75 degreeC for 3 hours, and obtained polyisocyanate hardener NCO-B1. IR analysis of NCO-B1 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-B1 was 7.4%, and therefore the isocyanurate group content was 12.3%. Solid content was 50.1%. In addition, the content of TDI (1) liberated from the GPC analysis was 0.2%.

Synthesis Example 9

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 329 g of ethyl acetate were added and stirred uniformly. 227.1g of polyol E was put in this, and it was made to react at 75 degreeC for 3 hours. IR analysis confirmed the presence of isocyanate groups and urethane groups in the reaction product, but not hydroxyl groups. The isocyanate group content of this reaction product was 7.4%.

Subsequently, 0.5 g of magnesium naphthenate was further added therein, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction, thereby obtaining a polyisocyanate curing agent NCO-B2. IR analysis of NCO-B2 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but no hydroxyl group. The isocyanate group content of NCO-B2 was 2.4%, and therefore the isocyanurate group content was 4.0%. Solid content was 50.0%. In addition, the content of TDI (1) liberated from GPC analysis was 0.4%.

Synthesis Example 10

After replacing the inside of the same reactor as in Synthesis Example 1 with nitrogen, 200 g of HDI and 98.8 g of polyol B were added and reacted at 75 ° C. for 3 hours. IR analysis confirmed the presence of isocyanate groups and urethane groups in the reaction product, but not hydroxyl groups. The isocyanate group content of this reaction product was 30.7%.

Subsequently, 0.22 g of potassium capricate and 0.03 g of phenol were charged therein, and isocyanurate reaction was performed at 50 ° C for 5 hours. Thereafter, 0.3 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction. The isocyanate group content at this time was 26.1%. Thereafter, the thin film was distilled off under conditions of 120 ° C and 13 kPa to remove liberated HDI to obtain a polyisocyanate curing agent NCO-B3. The yield was 55%. IR analysis of NCO-B3 confirmed the presence of an isocyanate group, an isocyanurate group and a urethane group, but not a hydroxyl group. The isocyanate group content of NCO-B3 was 5.2%, and therefore the isocyanurate group content was 9.7%. Solid content was 100.0%. In addition, the content of HDI liberated from GPC analysis was 0.4%.

Synthesis Example 11

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 100 g of TDI (1) and 101 g of ethyl acetate were added and stirred uniformly. 0.5 g of magnesium naphthenates were put in this, and isocyanurate-reacted at 75 degreeC for 5 hours. Thereafter, 0.05 g of phosphoric acid was added and stirred at 60 ° C for 1 hour to stop the isocyanurate reaction, thereby obtaining a polyisocyanate curing agent NCO-B4. IR analysis of NCO-B4 confirmed the presence of an isocyanate group and an isocyanurate group. The isocyanate group content of NCO-B4 was 8.5%, and therefore the isocyanurate group content was 15.5%. Solid content was 49.9%. In addition, the content of TDI (1) liberated from GPC analysis was 0.3%.

[Preparation of Polyisocyanate Curing Agent]

It mixed with the compounding (solid content conversion, g) shown in Tables 1-10, and prepared the polyisocyanate hardening | curing agent.

Stability over time

The obtained coupling agent mixed polyisocyanate hardener was stored for 1 month at 25 degreeC in the dark, and visual stability was judged visually.

Criteria

○: no change in appearance (solidification or occurrence of precipitates or suspended solids is not recognized)

X: Appears to change (solidification or occurrence of precipitates and suspended solids is recognized)

Synthesis of Resin for Subject

The symbol of the raw material used by the synthesis example 12 is as follows.

Polyol F: polyesterdiol obtained from ethylene glycol / neopentyl glycol = 1/1 and sebacic acid / isophthalic acid = 1/1 (each molar ratio), number average molecular weight = 2,000

Polyol G: diol which added (epsilon) -caprolactone to 2, 2- dimethylol butanoic acid, number average molecular weight = 500

DBTDL: Dibutyltin Dilauret

Synthesis Example 12

After replacing the inside of the reactor similar to the synthesis example 1 with nitrogen, 75g of 350g polyol G and 215g of ethyl acetate were prepared for polyol F, and it stirred uniformly. Subsequently, 75 g of MDI and 0.1 g of DBTDL were added thereto and reacted at 75 ° C. 285 g of ethyl acetate was added and stirred uniformly where the isocyanate group was not confirmed by IR analysis, and polyurethane resin PU-1 was obtained. Solid content was 50.0%.

[Evaluation of Adhesive]

Examples 1-40 and Comparative Examples 1-28

The main body and the hardening | curing agent were mix | blended in the ratio shown to Tables 1-10, laminated adhesives AD-1-68 were prepared, and various tests were done. These results are collectively shown in Tables 1-10.

Softening point measurement

The prepared laminated adhesive was cast on a release paper to have a dry thickness of about 100 μm, allowed to stand at 25 ° C. for 2 hours, and then placed in an 80 ° C. hot air dryer for 5 minutes, then taken out, and left at 35 ° C. for 16 hours to produce a laminated film. Created. This film was punched into the No. 2 dumbbell shape of JIS K6301, and it was set as the test piece. 49 kPa was applied to this test piece, and the softening point was measured at the temperature increase rate of 10 degree-C / min. The softening point is the temperature at which the test specimen elongated or was cut off.

Viscosity growth rate measurement

After mix | blending an adhesive agent, it put into the sample bin and stored this in the 25 degreeC constant temperature water tank, and after 1 hour, the viscosity was measured with the Brookfield viscometer. Let this be an initial viscosity. Then, after storing for 24 hours in a 25 degreeC constant temperature water bath, the viscosity was measured with the Brookfield viscometer. It evaluated by the increase rate (%) with respect to initial stage viscosity of the adhesive viscosity after this 24 hours.

◎: less than 10% viscosity increase

○: viscosity increase rate from 10 to 30%

△: viscosity increase rate 30 to 100%

X: viscosity increase more than 100% or gelation

Lamination test

1st method

Each of the laminating adhesives AD-1 to 13, a corona treated nylon (NY) film, a corona treated low density polyethylene (LLDPE) film was set in a dry laminate. The adhesive was then applied to the corona treated surface of the NY film with a gravure roll. The dry coating amount of an adhesive agent is 3.5 g / m <2>. The NY film to which the adhesive was applied was passed through a hot air dryer at 80 ° C. and adhered to the corona treated surface of the LLDPE film with a nip roll. Nip condition is 100 degreeC and 0.3 Mpa. Thereafter, curing was performed at 35 ° C. for 16 hours to obtain a laminated film.

The obtained laminated | multilayer film was cut into 15 mm width, and the T type peeling test was done. Peeling conditions were a tensile rate of 300 mm / min, the measuring atmosphere is 25 ℃, 50% RH.

Furthermore, the obtained laminated | multilayer film was cut | disconnected to the rectangle of 25 cm x 30 cm, NY surface was made outside, heat sealing three sides other than one short side on conditions of 220 degreeC, 0.3 MPa, and 1 second, and made a bag, A commercially available weak alkaline medical liquid synthetic detergent (trade name: Attack (trademark), a gauze agent) was added thereto, and the unsealed sides were heat sealed at 220 ° C., 0.3 MPa for 1 second. This was preserved at 50 ° C. for 2 weeks, after which the appearance was observed. Furthermore, the laminated | multilayer film was cut | disconnected to 15 mm width, and the T type peeling test was done. Peeling conditions were 300 mm / min tensile rate, 25 degreeC, 50% RH.

Used film

NY film: Toyobo, N-1102 (thickness: 15 micrometers)

LLDPE film: docerose, TUX-FCD (thickness: 130 μm)

(2) method

Laminated Adhesives AD-14 to 68, respectively, corona treated polyethylene terephthalate (PET) film, aluminum (AL) foil, corona treated unstretched polypropylene (CPP) film were set in a dry laminate. The adhesive was then applied to the corona treated surface of the PET film with a gravure roll. The dry coating amount of an adhesive agent is 3.5 g / m <2>. The PET film to which the adhesive was applied was passed through the hot air dryer at 80 ° C. and adhered to AL foil with a nip roll. Nip condition is 100 degreeC and 0.3 Mpa. Next, the adhesive was applied to the AL foil surface with a gravure roll. The dry coating amount of an adhesive agent is 3.5 g / m <2>. The laminated | multilayer film of PET film / AL foil which apply | coated the adhesive agent passed through the 80 degreeC hot air dryer, and adhere | attached the corona treatment surface of CPP film with a nip roll. Nip condition is 100 degreeC and 0.3 Mpa. Thereafter, curing was performed at 35 ° C. for 16 hours to obtain a laminated film.

The obtained laminated | multilayer film was cut into 15 mm width, and the T type peeling test was done. Peeling conditions were 300 mm / min tensile rate, 25 degreeC, 50% RH.

Furthermore, the obtained laminated | multilayer film was cut | disconnected to the rectangle of 25 cm x 30 cm, PET side was made outside, heat-sealing three sides other than one short side on 180 degreeC, 0.3 MPa, and 1 second conditions, and made a bag, A mixture of tomato ketchup / salad oil / vinegar = 1/1/1 (weight ratio) was added and the unsealed sides were heat sealed at 180 ° C., 0.3 MPa for 1 second. After retort-processing this at 120 degreeC for 30 minutes, the laminated | multilayer film was cut | disconnected in 15 mm width, and the T type peeling test was done. Peeling conditions were 300 mm / min tensile rate, 25 degreeC, 50% RH.

Used film

PET film: Toyobo, E-5100 (thickness: 12 μm)

AL foil: Made of Toyo Aluminum, Aluminhak C (thickness: 9 μm)

CPP film: docerose, CP RXC-11 (thickness: 70 μm)

In Tables 1 to 10,

C-L: Coronate® L

Polyisocyanate made by Nippon Polyurethane Industry, urethane-modified TDI with TMP

Isocyanate group content = 13.2%, solid content = 75%, ethyl acetate solution

C-HL: Coronate HL

Polyisocyanate made by Nippon Polyurethane Industry, urethane-modified HDI in TMP

Isocyanate group content = 12.8%, solid content = 75%, ethyl acetate solution

NY215A: Mytech (registered trademark) NY215A

Polyisocyanate made by Mitsubishi Chemical, urethane-modified IPDI with TMP

Isocyanate group content = 10.5%, solid content = 75%, ethyl acetate solution

D-110N: Takenate (registered trademark) D-110N

Takeda Pharmaceutical Co., Ltd. Polyisocyanate with urethane-modified XDI in TMP

Isocyanate group content = 11.5%, solid content = 75%, ethyl acetate solution

D-120N: Takenate (registered trademark) D-120N

Takeda Pharmaceutical Co., Ltd., Polyisocyanate modified urethane with H ₆ XDI

Isocyanate group content = 11.0%, solid content = 75%, ethyl acetate solution

TEA: triethylamine

SC-1: γ-isocyanatepropyltrimethoxysilane

SC-2: γ-isocyanatepropyltriethoxysilane

SC-3: γ-aminopropyltrimethoxysilane

As understood from Tables 1, 3 and 4, the lamination adhesives AD1 to 7 and 14 to 26 of Examples 1 to 20 were small in viscosity increase rate and sufficient pot life even after blending the main material and the curing agent. Nevertheless, since the softening point is high and the reactivity is high, the crosslinking reaction is considered to have sufficiently proceeded under the film production conditions (25 ° C × 2 hours + 80 ° C × 5 minutes + 35 ° C × 16 hours). Moreover, in actual lamination | stacking adhesion | attachment, sufficient adhesiveness was exhibited by the short aging time of 16 hours (1/3 or less of conventional aging time).

It is considered from Table 2 that the crosslinking reaction proceeded sufficiently because the curing agents AD-8 and 9 of Comparative Examples 1 and 2 had a high softening point. However, since the molecular weight of the polyol is not suitable, the adhesion performance is low. Moreover, the comparative example 4 which does not use the polyol also had the same tendency as the comparative examples 1 and 2. In Comparative Examples 3 and 5, since the softening point is low, it is considered that the crosslinking reaction does not sufficiently proceed under the above-mentioned film making conditions. Moreover, although adhesive strength was favorable, since it did not harden | cure hardly, the detergent resistance was inadequate. In Comparative Example 6, the curing agent AD-13 of Comparative Example 5 was used in combination with a catalyst. The reactivity between the main agent and the curing agent was improved, but the pot life was shortened.

In addition, since Table 4 shows that the hardening | curing agents AD-27 and 28 of Comparative Examples 7 and 8 have a high softening point, it is thought that crosslinking reaction fully advanced. However, since the molecular weight of the polyol is not suitable, the adhesion performance is low. Moreover, the comparative example 10 which does not use the polyol also had the same tendency as the comparative examples 7 and 8. In Comparative Examples 9 and 11, since the softening point is low, it is considered that the crosslinking reaction did not sufficiently proceed under the film production conditions described above. Moreover, although adhesive strength was favorable, since it was not hardening | curing, the adhesive strength after retort was inadequate. In Comparative Example 12, the curing agent AD-31 of Comparative Example 11 was used in combination with the catalyst, but the reactivity was improved, but the pot life was shortened, and it is difficult to use considering the actual adhesive application process.

From Tables 5-10, the time-lapse stability of the polyisocyanate hardener which added the silane coupling agent which has an amino group was bad, and neither pot life nor aging time were compatible.

As described above, since the polyisocyanate curing agent of the present invention can shorten the aging time without shortening the pot life, the production efficiency of the laminated film is significantly improved. The laminated adhesive using the polyisocyanate hardening | curing agent of this invention has favorable adhesiveness, and the laminated | multilayer film obtained can endure high retort. In addition, the polyisocyanate curing agent of the present invention can be used not only for laminating adhesives, but also for ordinary two-component adhesives, coatings, magnetic recording media, coating agents, primers, printing inks, sealing materials and the like.

Claims (25)

(a) having an isocyanurate group and a urethane group obtained by reacting an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) An isocyanate group terminal prepolymer is contained, The polyisocyanate hardening | curing agent for laminated adhesives characterized by the above-mentioned. The method of claim 1, The polyisocyanate curing agent for laminated adhesive, wherein the organic polyisocyanate is (a1) aromatic diisocyanate and the active hydrogen group-containing compound is (a2) a diol compound having a number average molecular weight of 100 to 2,000. (a) having an isocyanurate group and a urethane group obtained by reacting an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) An isocyanate group terminal prepolymer and (B) an isocyanate group terminal prepolymer containing a urethane group are contained, The polyisocyanate hardening | curing agent for laminated adhesives characterized by the above-mentioned. The method of claim 3, wherein The polyisocyanate curing agent for laminated adhesive, wherein the organic polyisocyanate is (a1) aromatic diisocyanate and the active hydrogen group-containing compound is (a2) a diol compound having a number average molecular weight of 100 to 2,000. The method of claim 3, wherein The polyisocyanate hardening | curing agent for laminated adhesives whose said component (B) is an isocyanate group terminal prepolymer which has a urethane group obtained by making (b1) organic diisocyanate and (b2) polyhydric alcohol react. (a) having an isocyanurate group and a urethane group obtained by reacting an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) An isocyanate group terminal prepolymer and (C) the silane coupling agent represented by following formula (1) are contained, The polyisocyanate hardening | curing agent for laminated adhesives characterized by the above-mentioned. Formula 1 OCN- (CH ₂ ) _m -Si (OR) ₃ In the above formula, R means a methyl group or an ethyl group, m is an integer of 1-5. The method of claim 6, The polyisocyanate curing agent for laminated adhesive, wherein the organic polyisocyanate is (a1) aromatic diisocyanate and the active hydrogen group-containing compound is (a2) a diol compound having a number average molecular weight of 100 to 2,000. (a) having an isocyanurate group and a urethane group obtained by reacting an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) An isocyanate group terminal prepolymer, (B) an isocyanate group terminal prepolymer having a urethane group, and (C) a silane coupling agent represented by the following general formula (1). Formula 1 OCN- (CH ₂ ) _m -Si (OR) ₃ In the above formula, R means a methyl group or an ethyl group, m is an integer of 1-5. The method of claim 8, The polyisocyanate curing agent for laminated adhesive, wherein the organic polyisocyanate is (a1) aromatic diisocyanate and the active hydrogen group-containing compound is (a2) a diol compound having a number average molecular weight of 100 to 2,000. The method of claim 8, The polyisocyanate hardening | curing agent for laminated adhesives whose said component (B) is an isocyanate group terminal prepolymer which has a urethane group obtained by making (b1) organic diisocyanate and (b2) polyhydric alcohol react. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 1, (i) urethane-forming an organic polyisocyanate containing at least (a1) aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to produce a urethane-modified polyisocyanate. fair; And (ii) isocyanurating the urethane-modified polyisocyanate to produce an isocyanate group-end prepolymer having an isocyanurate group and a urethane group. . The method of claim 11, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 1, (iii) isocyanurating an organic polyisocyanate containing at least aromatic diisocyanate to produce isocyanurate-modified polyisocyanate; And (iv) urethane-forming the isocyanurate-modified polyisocyanate and (a2) an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to (A) an isocyanate having an isocyanurate group and a urethane group A method for producing a polyisocyanate curing agent for a laminated adhesive, comprising the step of producing a terminal terminal prepolymer. The method of claim 13, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 1, (v) urethanization reaction and isocyanurate reaction simultaneously with an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) And (A) a step of producing an isocyanate group terminal prepolymer having an isocyanurate group and a urethane group. The method of claim 15, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 3, (i) urethane-forming an organic polyisocyanate containing at least (a1) aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to produce a urethane-modified polyisocyanate. fair; (ii) isocyanurating the urethane-modified polyisocyanate to produce (A) an isocyanate group-end prepolymer having an isocyanurate group and a urethane group; And (vi) A method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group. . The method of claim 17, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. The method of claim 17, A method for producing a polyisocyanate curing agent for a laminated adhesive, wherein the component (B) is an isocyanate group terminal prepolymer having a urethane group, which is obtained by reacting an organic diisocyanate with (b1) a polyhydric alcohol. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 3, (iii) isocyanurating an organic polyisocyanate containing at least aromatic diisocyanate to produce isocyanurate-modified polyisocyanate; (iv) urethaneization of the isocyanurate-modified polyisocyanate and (a2) an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 to (A) an isocyanate having an isocyanurate group and a urethane group Preparing a group terminal prepolymer; And (vii) a method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group . The method of claim 20, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. The method of claim 20, A method for producing a polyisocyanate curing agent for a laminated adhesive, wherein the component (B) is an isocyanate group terminal prepolymer having a urethane group, which is obtained by reacting an organic diisocyanate with (b1) a polyhydric alcohol. As a manufacturing method of the polyisocyanate hardener for laminated adhesive of Claim 3, (v) urethanization reaction and isocyanurate reaction simultaneously with an organic polyisocyanate containing at least an aromatic diisocyanate and an active hydrogen group-containing compound containing at least a diol compound having a number average molecular weight of 100 to 2,000 (a2) (A) producing an isocyanate group terminal prepolymer having an isocyanurate group and a urethane group; And (viii) A method for producing a polyisocyanate curing agent for a laminated adhesive comprising the step of mixing the isocyanate group terminal prepolymer (A) with isocyanurate group and urethane group and (B) the isocyanate group terminal prepolymer with urethane group. . The method of claim 23, The organic polyisocyanate is a (a1) aromatic diisocyanate, and the active hydrogen group-containing compound is a (a2) diol compound having a number average molecular weight of 100 to 2,000. The method of claim 23, A method for producing a polyisocyanate curing agent for a laminated adhesive, wherein the component (B) is an isocyanate group terminal prepolymer having a urethane group, which is obtained by reacting an organic diisocyanate with (b1) a polyhydric alcohol.