WO2015008822A1 - ラミネート接着剤組成物 - Google Patents
ラミネート接着剤組成物 Download PDFInfo
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- WO2015008822A1 WO2015008822A1 PCT/JP2014/069011 JP2014069011W WO2015008822A1 WO 2015008822 A1 WO2015008822 A1 WO 2015008822A1 JP 2014069011 W JP2014069011 W JP 2014069011W WO 2015008822 A1 WO2015008822 A1 WO 2015008822A1
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- WIPO (PCT)
- Prior art keywords
- adhesive composition
- polyol
- aminosilane
- laminate adhesive
- coupling agent
- Prior art date
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Classifications
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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
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to an adhesive composition and a laminating method. More specifically, laminating various plastic films, metal vapor-deposited films, aluminum foils, etc., and laminating two-component mixed adhesive composition for use in producing composite films mainly used for packaging materials such as foods, pharmaceuticals, and detergents. Related to things.
- Laminate adhesives are generally cured by polyol / isocyanate, and are often used for high-functional applications such as retort applications. These adhesives are often bonded to a transparent vapor-deposited film and a sealant from the bonding of an aluminum foil and a sealant so that the contents of the food can be confirmed from the packaging material. Therefore, in order to provide adhesion between these films and the deposited film, it is common to add a silane coupling agent such as epoxy silane or aminosilane silane to the adhesive (for example, see Patent Document 1). ). However, if the amount of epoxy silane is increased in order to maintain adhesion, the dissolution of epoxy silane into the food will increase. Further, when the same adhesive is used for laminating a film without vapor deposition, the elution of the silane coupling agent is greater than that of the vapor deposition adhesive, and the adhesive needs to be changed depending on the construction.
- a silane coupling agent such as epoxy silane or aminosilane silane
- an object of the present invention is to provide an adhesive for a flexible package comprising a polyol and an isocyanate, which reduces the amount of chemical substances eluted into food while maintaining the adhesion of the transparent vapor-deposited film. It is to provide.
- the present inventor As a result of intensive studies, maintains the adhesiveness when a mixture or reaction product of epoxysilane (c1) and aminosilane (c2) is used as the silane coupling agent (C).
- the present inventors have found that elution of the silane coupling agent (C) can be suppressed and completed the present invention.
- the present invention is a laminate adhesive composition containing a polyol, a polyisocyanate, and a silane coupling agent (C), wherein the silane coupling agent (C) is an epoxy silane (c1) and an aminosilane (c2).
- the laminate adhesive composition is characterized in that it is a mixture or a reaction product.
- the present invention comprises the following items. 1. A laminate adhesive composition containing a polyol (A), a polyisocyanate (B), and a silane coupling agent (C), A laminate adhesive composition, wherein the silane coupling agent (C) is a mixture of epoxy silane (c1) and aminosilane (c2); 2. The silane coupling agent (C) is a reaction product obtained by reacting a mixture of epoxy silane (c1) and aminosilane (c2).
- the polyol (A) is a polyester polyol or a polyether polyol. Or 2.
- Examples of the polyol resin (A) used in the present invention include a polyol (a1) described later, a polyester polyol obtained by reacting a polyol (a1) with a polycarboxylic acid described later, or ethylene glycol, diethylene glycol, Ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and other compounds having two active hydrogen atoms as an initiator for ethylene
- Examples thereof include polyethers obtained by addition polymerization of monomers such as oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene.
- polyol (a1) examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexane Diol, 1,4-cyclohexanedimethanol, triethylene glycol, polycaprolactone diol, dimer diol, bisphenol A, hydrogenated bisphenol A, etc.
- Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as coles, propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ethylene glycol, diethylene glycol, triethylene glycol Ethylene oxide with a compound having two active hydrogen atoms such as propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Examples thereof include polyethers obtained by addition polymerization of monomers such as propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene.
- cyclic ester compounds such as coles, propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone,
- the equivalent ratio [(B) / (A)] of the hydroxyl group equivalent of the polyol resin (A) and the isocyanate equivalent of the polyisocyanate (B) is preferably 0.5 to 5.0.
- the silane coupling agent (C) used in the present invention is a mixture of epoxy silane (c1) and aminosilanes (c2), which will be described later, or a reaction product obtained by reaction.
- aminosilane (c2) examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropylmethyldioxysilane.
- the reaction ratio of the epoxysilane (c1) and the aminosilane (c2) is not particularly limited.
- the molar ratio of the epoxysilane (c1) and aminosilane (c2) [(c1) / (c2)] The ratio is preferably 1/1 to 3/1, and particularly preferably 2/1.
- the silane coupling agent (C) is preferably added in an amount of 0.1 to 2 parts by mass per 100 parts by mass of polyol.
- the amount of elution of the silane coupling agent (C) can be further reduced by adding a phosphoric acid derivative or a styrene-maleic anhydride copolymer to the laminate adhesive composition of the present invention.
- Examples of the phosphoric acid derivative include orthophosphoric acid and polyphosphoric acid.
- the styrene-maleic anhydride copolymer is represented, for example, by the following formula (1).
- m is preferably 1 to 8
- n is preferably 8 to 12.
- the styrene-maleic anhydride copolymer can be obtained by radical copolymerization of styrene and maleic anhydride by various methods. Moreover, a commercial item can also be utilized and examples include SMA3000, SMA1000, SMA2000, EF30, EF40, EF60, and EF80 manufactured by Sartomer Japan.
- the phosphoric acid derivative and the styrene-maleic anhydride copolymer can be used alone or in combination.
- the blending ratio when both are used is independently 0.1 to 1.0 part by mass of a phosphoric acid derivative per 100 parts by mass of polyol, and styrene-maleic anhydride copolymer 1. It is preferable to add 0 to 10 parts by mass.
- the laminate adhesive composition of the present invention may contain other additives other than those described above, if necessary.
- the additive include additives generally used in resin compositions that form films and coating films.
- additives include leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles based on polymethyl methacrylate; antifoaming agents; anti-sagging agents; wetting and dispersing agents; silane coupling agents; Ultraviolet absorber; Metal deactivator; Peroxide decomposing agent; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust inhibitor; Fluorescent brightener; Inorganic heat absorber; Agents; dehydrating agents; and the like.
- the laminate adhesive composition of the present invention is usually prepared by preparing a main ingredient premix in which components other than the polyisocyanate compound that is a curing agent are blended in advance, and mixing this with the polyisocyanate compound. I can do it.
- the adhesive composition is applied to a substrate with a gravure coater, a die coater or a lip coater, and dried and bonded to another substrate.
- the coating width can be freely adjusted by deckles attached to both ends of the die or the lip portion.
- the application amount of the adhesive is about 0.5 to 6.0 g / m 2 , preferably 1.0 to 4.0 g / m 2 .
- part indicates “part by mass”.
- the pressure was reduced to 10 mmHg or less and held for 1.5 hours to complete the esterification reaction, and an intermediate polyester polyol having a hydroxyl value of 28 was obtained.
- To 100 parts of the obtained intermediate polyester polyol 8.9 parts of isophorone diisocyanate was added and heated to 120 ° C. to carry out a urethanization reaction until NCO% was 3.1 to obtain a polyester urethane polyisocyanate. .
- This was diluted with 111.9 parts of ethyl acetate and then the temperature was lowered to 40 ° C. and kept at 50 ° C. for about 1 hour to obtain a polyurethane polyester polyol resin solution U having a nonvolatile content of 60%.
- Epoxysilane (c1) is 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone)
- aminosilane (c2) is 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone)
- phosphoric acid is As a 85% phosphoric acid styrene-maleic anhydride copolymer (SMA) manufactured by Kojun Pharmaceutical Co., Ltd., a reagent having a Mw of 7,500 manufactured by Wako Pure Chemical Industries, Ltd. was used.
- Example 1 (Example 1) to (Example 8) With the composition shown in Table 1, polyol resin solution U, aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), silane compound, phosphoric acid, and styrene maleic acid were blended to prepare a blend having a solid content of 30%. About the obtained compound, a PET film and a polypropylene film were bonded together by the method shown below, and an elution test and a peel strength measurement were performed. The obtained results are shown in Table 1.
- the reactants used in this example are the reactants A to E obtained in Production Example 3.
- Example 9 (Example 9) to (Example 11) With the compositions shown in Table 2, dissolution tests and peel strength measurements were performed in the same manner as in Examples 1-8. The obtained results are shown in Table 2.
- the reactants used in this example are the mixtures A to C obtained in Preparation Example 4.
- Comparative Example 1 (Comparative Example 1) to (Comparative Example 3) Except having used the raw material of the composition shown in Table 3, it carried out similarly to Example 1, and prepared the compounding liquid and implemented various tests.
- Comparative Example 4 as described in “Patent No. 4226852”, aminosilane was added to polyol U and stirred for 1 hr to prepare polyol UA.
- epoxy silane was added to polyisocyanate I in advance and stirred for 1 hr. Adjust polyisocyanate IE. A blending solution of these polyol and polyisocyanate was prepared in the same manner as in Example 1. The obtained results are shown in Table 3.
- the laminate was affixed with PET film (Toyobo E5100 12 ⁇ m) and CPP (Toray Film Processing Co., Ltd .; ZK93KM 70 ⁇ m) with an adhesive (solid content 3.5 g / m 2 ) and stored at 40 ° C. for 72 hours. .
- the dissolution test was carried out according to EN13130.
- a pouch was prepared so that the contact portion of the contents was 200 cm 2 and filled with 100 mL of 95% ethanol as a simulated food solution.
- the prepared pouch was stored at 60 ° C. for 10 days, 100 mL was concentrated to 5 mL, and the silane compound was quantified by GC-MS.
- the unit of elution amount was calculated in terms of EU standard mg / kg-food.
- the lower limit of quantification of the silane compound is 0.001 mg / kg-food.
- ⁇ Measurement conditions> Using a tensile tester at an ambient temperature of 25 ° C., the peeling speed is set to 300 mm / min, the tensile strength when measured by the T-type peeling method is the adhesive strength, and the unit of the adhesive strength is N / 15 mm. .
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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
Description
しかしながら、密着性を保持するためにエポキシシランを増量すれば、エポキシシランの食品への溶出は増大する。さらに、同じ接着剤を蒸着のないフィルムのラミネートに使用するとシランカップリング剤の溶出は蒸着構成の接着剤より多くなり、構成により接着剤を交換する必要がある。
1.ポリオール(A)、ポリイソシアネート(B)、及びシランカップリング剤(C)を含有するラミネート接着剤組成物であって、
前記シランカップリング剤(C)が、エポキシシラン(c1)とアミノシラン(c2)の混合物であることを特徴とするラミネート接着剤組成物、
2.前記シランカップリング剤(C)がエポキシシラン(c1)とアミノシラン(c2)との混合物を反応させた反応物である1.に記載のラミネート接着剤組成物、
3.前記ポリオール(A)がポリエステルポリオール、又はポリエーテルポリオールである1.又は2.に記載のラミネート接着剤組成物、
4.更に、リン酸誘導体、又はスチレン-無水マレイン酸系共重合体を含有する1.~3.の何れかに記載のラミネート接着剤組成物、
5.エポキシシラン(c1)とアミノシラン(c2)のモル比が、1/1~3/1の範囲である1.~4.の何れかに記載のラミネート接着剤組成物。
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 10.0部、ネオペンチルグリコール 21.1部、1,6-ヘキサンジオール 10.0部、ツノダイム216 8.0部、イソフタル酸21.5部、テレフタル酸21.5部、アジピン酸23.4部及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、水酸基価28の中間体ポリエステルポリオールを得た。得られた中間体ポリエステルポリオールの100部に対し、イソホロンジイソシアネートを8.9部加え120℃に加熱してNCO%が3.1になるまでウレタン化の反応を行ってポリエステルウレタンポリイソシアネートを得た。これを酢酸エチル111.9部で希釈した後に40℃まで温度を下げて、50℃で約1時間保持し、不揮発分60%のポリウレタンポリエステルポリオール樹脂溶液Uを得た。
エポキシシラン(c1)は3-グリシドキシプロピルトリメトキシシラン(信越シリコーン社製KBM-403)、アミノシラン(c2)は3-アミノプロピルトリメトキシシラン(信越シリコーン社製KBM-903)、燐酸は和光純薬工業社製85%リン酸 スチレン-無水マレイン酸共重合体(SMA)は和光純薬工業社製Mw7,500の試薬を使用した。
エポキシシラン(c1)とアミノシラン(c2)の反応物は、エポキシシラン(c1)とアミノシラン(c2)を、モル比0.5:1、1:1、2:1、3:1、4:1になるようにフラスコに投入し、40℃で7時間反応させ、反応物A、B、C、D、Eを得た。
エポキシシラン(c1)とアミノシラン(c2)を、モル比1:1、2:1、3:1、になるようにフラスコに投入し、エポキシシラン(c1)とアミノシラン(c2)を混合し、混合物A、B、Cを得た。
表1に示す組成で、ポリオール樹脂溶液U、芳香族ポリイソシアネート(DIC株式会社製KW-75)、シラン化合物、燐酸、スチレンマレイン酸を配合し、固形分30%の配合物を調製した。得られた配合物について、下記に示す方法でPETフィルムとポリプロピレンフィルムを貼り合せ、溶出試験、ピール強度の測定を行った。得られた結果を表1に示す。本実施例で使用した反応物は、前記製造例3で得た反応物A~Eである。
表2に示す組成で、実施例1~8と同様に、溶出試験、ピール強度の測定を行った。得られた結果を表2に示す。本実施例で使用した反応物は、前記製造例4で得た混合物A~Cである。
表3に示す組成の原料を用いた以外は、実施例1と同様にして、配合液を調製し、各種試験を実施した。尚、比較例4は「特許第4226852号」の請求項記載の通り、ポリオールUにアミノシランを投入し、1hr攪拌してポリオールUAを調整した。一方で、ポリイソシネートIに予めエポキシシランを投入し1hr攪拌し。ポリイソシアネートIEを調整。これらのポリオールとポリイソシアネートを実施例1と同様に配合液を調整した。得られた結果を表3に示す。
ラミネート物はPETフィルム(東洋紡社製E5100 12μm)とCPP(東レフィルム加工社製;ZK93KM 70μm)を接着剤(固形分は3.5g/m2)にて張り合わせ、40℃-72時間エージング保存した。溶出試験はEN13130に従って実施した。内容物の接触部分が200cm2、になるようにパウチを作成し、食品疑似溶液として95%エタノールが100mLを充填した。作成したパウチは60℃-10日間で保存後、100mLを5mLまで濃縮しGC-MSでシラン化合物を定量した。溶出量の単位はEU基準のmg/kg-foodで算出した。シラン化合物の定量下限は0.001mg/kg-foodである。
<測定条件>
GC-MS 島津製作所製 GC2100A
カラム;ポリジメチルシロキサン系
塗工液の色相はガードナー比色計で色相を測定した。
ラミネート物はPETフィルム(東洋紡社製E5100 12μm)、アルミ箔(12μm)、CPP(東レフィルム加工社製;ZK93KM 70μm)を接着剤(固形分は3.5g/m2)にて張り合わせ、40℃-72hrのエージング保存した。その後、内容物の接触部分が200cm2となるようにパウチを作成し、食品疑似溶液内容物に食用酢:ミートソース:日本酒=1:1:1の溶液を50mL充填した。充填したパウチはスチーム殺菌処理を135℃-30min実施し、内容物を除去したヒートシール部のピール強度を測定した。
<測定条件>
雰囲気温度25℃で引張り試験機を用いて、剥離速度を300mm/分に設定し、T型の剥離方法で測定した際の引張り強度を接着強度とし、接着強度の単位は、N/15mmとする。
表1、3の結果の通り、エポキシシランとアミノシランの反応物を用いた実施例1~8は、エポキシシランのみの比較例1に比べ、エポキシシランの溶出量が小さくなった。アミノシランを添加した比較例2はシラン化合物の溶出は確認できなかったが塗工液が着色していた。
また、実施例5~8ではリン酸、又はスチレン-無水マレイン酸樹脂を添加することにより、更にエポキシシランの溶出を減ずることができた。
更に、エポキシシランとアミノシランの混合物を用いた実施例9~11では、塗工液の色相及び場合にも、反応物を用いたのと同様に好成績であった。
Claims (5)
- ポリオール(A)、ポリイソシアネート(B)、及びシランカップリング剤(C)を含有するラミネート接着剤組成物であって、
前記シランカップリング剤(C)が、エポキシシラン(c1)とアミノシラン(c2)の混合物であることを特徴とするラミネート接着剤組成物。 - 前記シランカップリング剤(C)がエポキシシラン(c1)とアミノシラン(c2)との混合物を反応させた反応物である請求項1に記載のラミネート接着剤組成物。
- 前記ポリオール(A)がポリエステルポリオール、又はポリエーテルポリオールである請求項1又は2に記載のラミネート接着剤組成物。
- 更に、リン酸誘導体、又はスチレン-無水マレイン酸系共重合体を含有する請求項1~3の何れかに記載のラミネート接着剤組成物。
- エポキシシラン(c1)とアミノシラン(c2)のモル比が、1/1~3/1の範囲である請求項1~4の何れかに記載のラミネート接着剤組成物。
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US14/905,582 US20160152880A1 (en) | 2013-07-19 | 2014-07-17 | Laminate adhesive composition |
CN201480039935.9A CN105392858A (zh) | 2013-07-19 | 2014-07-17 | 层压粘接剂组合物 |
JP2015506033A JP5761478B2 (ja) | 2013-07-19 | 2014-07-17 | ラミネート接着剤組成物 |
EP14825596.1A EP3023471A4 (en) | 2013-07-19 | 2014-07-17 | Laminate adhesive composition |
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WO2017096343A1 (en) * | 2015-12-04 | 2017-06-08 | Lord Corporation | Primer for pressure sensitive adhesive |
JP2020176226A (ja) * | 2019-04-19 | 2020-10-29 | 東洋インキScホールディングス株式会社 | 接着剤組成物及びその製造方法、積層フィルム並びに包装体 |
WO2021024981A1 (ja) * | 2019-08-06 | 2021-02-11 | 凸版印刷株式会社 | 硬化剤、2液型接着剤、接着剤組成物、硬化物、積層体及びその製造方法、包装材、並びに包装体 |
WO2021159300A1 (en) * | 2020-02-12 | 2021-08-19 | Dic Corporation | Adhesive composition, laminate, and package |
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IT201900022356A1 (it) * | 2019-11-28 | 2021-05-28 | Dow Global Technologies Llc | Composizione adesiva |
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JPWO2021024981A1 (ja) * | 2019-08-06 | 2021-09-13 | 凸版印刷株式会社 | 硬化剤、2液型接着剤、接着剤組成物、硬化物、積層体及びその製造方法、包装材、並びに包装体 |
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EP3023471A4 (en) | 2017-03-08 |
EP3023471A1 (en) | 2016-05-25 |
JP5761478B2 (ja) | 2015-08-12 |
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