WO2017138399A1 - 低エネルギー表面基材用接着剤組成物 - Google Patents
低エネルギー表面基材用接着剤組成物 Download PDFInfo
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/56—Non-aqueous solutions or dispersions
Definitions
- the present invention relates to an organic solvent solution type primer / adhesive composition that exhibits good adhesion performance to a low energy surface base material represented by polyolefin, especially a polyethylene base material.
- Patent Document 1 P139 “2.1 Current Status of Adhesion Technology”. Specific examples thereof include Patent Documents 1 to 5.
- Patent Documents 1 and 2 and Non-Patent Document 1 are not yet highly versatile at present.
- Patent Documents 3, 4 and 5 each propose a versatile resin based on a SEBS elastomer and an acid addition-modified propylene-butene-ethylene copolymer. It cannot be said that the adhesiveness is sufficient for the material.
- the present invention provides an adhesive composition that exhibits good adhesion performance to various olefin substrates, particularly polyethylene substrates, and is excellent in storage stability at low temperatures (20 ° C. and 15 ° C.). It is intended to provide.
- the present invention contains a modified polyethylene copolymer (component A) having a melting point of less than 80 ° C., a terpene tackifier (component B), and an organic solvent (component C), and 100 parts by weight of component A.
- component A a modified polyethylene copolymer having a melting point of less than 80 ° C.
- component B a terpene tackifier
- component C an organic solvent
- the terpene tackifier (component B) is preferably a terpene phenol resin modified with phenol.
- the organic solvent (C component) is preferably an alicyclic hydrocarbon compound and / or an aromatic hydrocarbon compound, and the A component and the B component occupy in the total weight of these A component, B component, and C component.
- the total weight ratio of is preferably 20% by weight or less.
- the polypropylene resin (component D) is contained in a range of less than 15 parts by weight with respect to 100 parts by weight of the component A.
- the adhesive composition of the present invention contains a resin having a polyethylene skeleton (modified polyethylene copolymer: component A) as a main component, and further contains a specific tackifier (component B) at a predetermined ratio.
- component A modified polyethylene copolymer
- component B specific tackifier
- LDPE density polyethylene substrate
- HDPE high density polyethylene substrate
- the stability of the organic solvent solution at low temperatures (20 ° C. and 15 ° C.) is exhibited by the melting point of the A component being less than 80 ° C. and the inclusion of a predetermined amount of the B component.
- the modified polyethylene copolymer (hereinafter also simply referred to as “component A”) used in the present invention is an ethylene- ⁇ -olefin copolymer, acrylic acid, alkyl acrylate ester, ⁇ , ⁇ -unsaturated carboxylic acid. And a copolymer of ethylene and at least one selected from the group consisting of acid anhydrides thereof.
- the ethylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with ethylene.
- ⁇ -olefin for example, one kind or several kinds of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like can be used. Of these, propylene and 1-hexene are preferable.
- the ratio of the ethylene component to the ⁇ -olefin component of the ethylene- ⁇ -olefin copolymer is not particularly limited, but the ethylene component is preferably 50 mol% or more, more preferably more than 50 mol%. .
- the ethylene- ⁇ -olefin copolymer polymerized using a metallocene-based catalyst has uniform crystallinity and is free from organic solvents. It is preferable because of its excellent solubility.
- the copolymerization amount of acrylic acid is preferably 0.1% by weight or more, and more preferably 1% by weight or more. Moreover, 5 weight% or less is preferable and 3 weight% or less is more preferable. If it is less than 0.1% by weight, the compatibility with the component B may be lowered, and if it exceeds 5% by weight, the adhesion to the polyethylene substrate may be lowered. Further, the copolymerization amount of alkyl acrylate is preferably 10% by weight or more, and more preferably 20% by weight or more. Moreover, 40 weight% or less is preferable and 30 weight% or less is more preferable.
- the at least one kind of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydride thereof is not particularly limited, and examples thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
- acid anhydrides are preferable, maleic anhydride and itaconic anhydride are more preferable, and maleic anhydride is more preferable.
- the copolymerization amount of these acid components is preferably 0.1% by weight or more, and more preferably 1% by weight or more. Moreover, 5 weight% or less is preferable and 3 weight% or less is more preferable. If it is less than 0.1% by weight, the compatibility with the component B may be lowered, and if it exceeds 5% by weight, the adhesion to the polyethylene substrate may be lowered.
- these modified polyethylene copolymers can be used alone or in combination of two or more.
- These modified polyethylene copolymers must have a melting point of less than 80 ° C, preferably less than 70 ° C, more preferably less than 60 ° C. Above 80 ° C, the stability of the organic solvent solution at low temperatures may be extremely poor.
- a minimum is not specifically limited, It is preferable that it is 30 degreeC or more, and it is more preferable that it is 40 degreeC or more. If it is less than 30 ° C., the cohesive strength of the resin is too low, and sufficient adhesive strength may not be obtained.
- Examples of commercially available products of these modified polyethylene copolymers include the following. There is “Kernel (registered trademark)” of Nippon Polyethylene Co., Ltd. as an ethylene- ⁇ -olefin copolymer polymerized with a metallocene catalyst. Examples include KS340T (melting point: 60 ° C.) and KJ640T (melting point: 58 ° C.). Among these, “KJ640T” having the lowest melting point is most preferable because it is excellent in stability of the organic solvent solution at low temperatures.
- the molecular weight of the component A of the present invention is preferably 0.1 g / 10 min or more, more preferably 1 g / 10 min or more, further preferably 1.5 g / 10 min or more, as a melt flow rate (MFR) value, 2 g / 10 min.
- MFR melt flow rate
- the above is particularly preferable.
- 100 g / 10 minutes or less are preferable, 50 g / 10 minutes or less are more preferable, 40 g / 10 minutes or less are still more preferable, 30 g / 10 minutes or less are especially preferable. If it exceeds 100 g / 10 min, the cohesive strength of the resin is lowered, and sufficient adhesive strength may not be obtained.
- the HDPE base material is a polyethylene resin base material having a density of 0.94 g / cm 3 or more, and particularly means a polyethylene base material in the vicinity of 0.95 g / cm 3 .
- the SP value of the tackifier is an approximate measure for judging compatibility.
- the SP value of the tackifier exhibiting good compatibility with the modified polyethylene copolymer (component A) is a value according to the calculation formula of Hoy, and is 8.60 to 8.90 (J / cm 3 ) 1/2 .
- ⁇ is the density of the polymer compound
- M is the molecular weight of the repeating structural unit of the polymer compound
- E is the molar aggregation energy constant of each structural unit constituting the polymer compound.
- the numerical value of E can use the numerical value published in various literature. Examples of documents in which numerical values are described include J. Paint Technology vol. 42 76-118 (1970).
- the higher the transparency of the dried coating film prepared by mixing the modified polyethylene copolymer and the tackifier the higher the compatibility.
- the transparency can be confirmed visually, but more accurately can be determined by using a HAZE meter (preferably 1.0 or less, more preferably 0.5 or less).
- a HAZE meter preferably 1.0 or less, more preferably 0.5 or less.
- the dynamic viscoelastic properties of the produced dry film are measured, and if the main dispersion peak of the loss elastic modulus (E ′′) is not broad compared with that before the tackifier compounding, it is judged that the compatibility is good. .
- the softening point of the tackifier is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 160 ° C. or lower, and more preferably 150 ° C. or lower.
- the number average molecular weight is preferably 500 or more, more preferably 700 or more, further preferably 800 or more, preferably 1800 or less, more preferably 1600 or less, and further preferably 1500 or less. If it is less than 500, the physical properties of the modified polyethylene copolymer (component A) resin coating may be reduced or the surface of the coating may bleed out. If it exceeds 1,800, the modified polyethylene copolymer (component A) Compatibility with the resin may deteriorate.
- the tackifier used in the present invention needs to be a terpene resin, and among them, a terpene phenol resin is more preferable.
- a terpene phenol resin examples include the Clearon (registered trademark) series manufactured by Yasuhara Chemical Co., Ltd.
- Specific examples of commercially available terpene phenol resins include YS Polyster (registered trademark) manufactured by Yasuhara Chemical Co., Ltd. ) Series.
- the SP values of “YS polystar T160”, “YS polystar T145”, “YS polystar T130”, “YS polystar T115”, “YS polystar T100”, and “YS polystar T80” are all 8.81 (J / cm). 3 ) 1/2
- the SP values of “YS polyster U130” and “YS polystar U115” are both 8.69 (J / cm 3 ) 1/2 .
- the compounding amount of the tackifier needs to be 10 parts by weight or more and 100 parts by weight or less, preferably 20 parts by weight or more and 80 parts by weight or less, with respect to 100 parts by weight of the modified polyethylene copolymer (component A). More preferably, it is 30 to 70 weight part, More preferably, it is 40 to 60 weight part. If the amount is less than 10 parts by weight, the compounding effect of the tackifier, that is, the adhesive property to the HDPE substrate and the solution stability at low temperature may not be obtained, and if it exceeds 100 parts by weight, the physical properties of the adhesive layer become brittle. Sometimes.
- Organic solvent used in the adhesive composition of the present invention
- organic solvent hereinafter also simply referred to as “C component”
- aromatic hydrocarbons such as toluene and xylene
- alicyclic hydrocarbons such as cyclohexane and methylcyclohexane.
- a mixture of these can be used as the main solvent.
- n-butyl acetate, ethyl acetate, 1-butanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, etc. can be mixed with the above main solvent in a range of less than 20% by weight with respect to the total organic solvent. .
- the total weight ratio of the A component and the B component in the total weight of the A component, the B component, and the C component is preferably 20% by weight or less, and more preferably 15% by weight or less.
- the total weight ratio of the A component, B component, and D component in the total weight of the A component, B component, C component, and D component is 20
- the content is preferably not more than wt%, more preferably not more than 15 wt%. If it exceeds 20% by weight, the deterioration of the stability of the organic solvent solution at low temperatures may be remarkable.
- a polypropylene resin (hereinafter, also simply referred to as “D component”) can be blended for the purpose of further improving the solubility in an organic solvent.
- the polypropylene resin (component D) include non-crystalline polypropylene resins and chlorinated modified polypropylene copolymers.
- the chlorinated modified polypropylene copolymer is preferably a polypropylene or propylene- ⁇ -olefin copolymer having a chlorine atom added to the side chain.
- the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
- ⁇ -olefin for example, one kind or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like can be used. Of these, 1-butene is preferred.
- the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not particularly limited, but the propylene component is preferably 50 mol% or more, more preferably more than 50 mol%. .
- chlorinated polypropylene copolymers examples include HARDLEN (registered trademark) DX series (“DX-526P”, “DX-530P”, etc.) manufactured by Toyobo Co., Ltd.
- examples of the amorphous polypropylene resin include El Modu (registered trademark) manufactured by Idemitsu Kosan Co., Ltd. (“El Modu S400”, “El Modu S600”, “El Modu S901”) and the like.
- Non-crystalline polypropylene resin is 10 ° C./min. Using a differential scanning calorimeter (DSC). That does not show a clear melting peak when the temperature is raised to -50 ° C. to 200 ° C. at a rate of.
- DSC differential scanning calorimeter
- the chlorine content of the chlorinated modified polypropylene copolymer is preferably 5% by weight or more, more preferably 8% by weight or more, and still more preferably 10% by weight or more. Moreover, it is preferable that it is 40 weight% or less, 35 mass% or less is more preferable, and 30 mass% or less is further more preferable. By setting it as the said range, favorable organic solvent solubility can be expressed.
- the weight average molecular weight (Mw) of the chlorinated modified polypropylene copolymer is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 60,000 to 150,000, and more preferably in the range of 80,000 to 130,000.
- the production method of the chlorinated modified polypropylene copolymer is not particularly limited, and for example, it can be obtained by dissolving polypropylene in a halogenated hydrocarbon such as chloroform and introducing chlorine.
- the production method of the above component D is not particularly limited, but the propylene- ⁇ -olefin copolymer polymerized using a metallocene catalyst has uniform crystallinity and excellent solubility in a solvent. ,preferable.
- the content of component D is preferably less than 15 parts by weight, more preferably 13 parts by weight or less, and even more preferably 11 parts by weight or less with respect to 100 parts by weight of component A. If the amount is too large, the adhesion to the polyethylene substrate may be impaired.
- the adhesive composition of the present invention contains a modified polyethylene copolymer (component A) having a melting point of less than 80 ° C., a terpene-based tackifier (component B), and an organic solvent (component C).
- component A a modified polyethylene copolymer having a melting point of less than 80 ° C.
- component B a terpene-based tackifier
- component C an organic solvent
- the B component is a composition having 30 to 100 parts by weight with respect to parts by weight.
- it is a composition which further contains the polypropylene resin (D component) of less than 15 weight part with respect to 100 weight part of A component depending on the case.
- the adhesive composition of the present invention can contain a curing agent as required.
- curing agent is not specifically limited,
- a polyfunctional isocyanate compound is mentioned.
- Specific examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexamethane diisocyanate, or alicyclic diisocyanate compounds and their respective addition multimeric compounds.
- aromatic diisocyanate compounds such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate and their respective addition multimeric compounds may be mentioned.
- various aliphatic polyfunctional epoxy compounds, alicyclic polyfunctional epoxy compounds, and aromatic polyfunctional epoxy compounds can also be blended.
- triphenylphosphine or various polyfunctional amine compounds may be added as a curing reaction accelerator.
- additives such as fillers, pigments, colorants, and antioxidants may be blended in the adhesive composition of the present invention as long as the adhesive performance is not deteriorated.
- the adhesive composition of the present invention does not substantially contain a rubber component. “Substantially free” is preferably 3% by weight or less in the adhesive composition, more preferably 1% by weight or less, still more preferably 0.1% by weight or less, and particularly preferably 0%. % By weight or less.
- the adhesive composition obtained in the present invention is excellent in adhesion to polyolefin resin substrates, particularly polyethylene resin substrates, primers, paints, inks and coating agents for painting, printing, adhesion and coating are used. Useful for adhesive applications.
- the polyolefin-based resin substrate may be appropriately selected from conventionally known polyolefin resins.
- polyethylene, polypropylene, ethylene-propylene copolymer, and the like can be used. You may mix
- composition weight ratio (tackifier content)
- the dried sample (resin) obtained by the measurement of the solid content concentration was dissolved in deuterated chloroform, and a nuclear magnetic resonance analyzer (NMR) “Gemini” manufactured by Varian Inc.
- NMR nuclear magnetic resonance analyzer
- the ratio of the modified polyethylene copolymer, the tackifier and the polypropylene resin was determined by 1 H-NMR analysis using “ ⁇ 400-MR”.
- the tip of the test piece is clamped by a chuck of a tensile tester (Orientec "RTM-100") and a 5kgf load cell is used, and a 90 ° peel test is performed by pulling it up and down at a pulling speed of 50mm / min in an atmosphere of 25 ° C. did.
- the average value of the five peel strengths obtained was calculated and shown in Table 2.
- Example 1 The following raw materials were charged into a 1 L glass flask equipped with a thermometer, a condenser, and a stirring rod, stirred at 80 ° C. for 1 hour, and the resin content was uniformly dissolved to prepare an adhesive composition.
- Kernel (registered trademark) KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- YS Polyster registered trademark
- T130 Yasuhara Chemical Co., Ltd. terpene phenol type tackifier
- MCH methylcyclohexane
- the solid content concentration, the modified polyethylene copolymer resin, and the content of the tackifier were measured, and the weight ratio of each component was determined from the results. It was shown in Table 1 with the measured value of melting
- the evaluation results of the peel test are shown in Table 2.
- Example 2 The following raw materials were charged into a 1 L glass flask equipped with a thermometer, a condenser, and a stirring rod, stirred at 80 ° C. for 1 hour, and the resin content was uniformly dissolved to prepare an adhesive composition.
- Lex Pearl ET350X Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- YS Polystar T130 Yasuhara Chemical Co., Ltd. terpene phenol tackifier
- Toluene 963 parts The solution was taken out after cooling, and the solution properties of the resulting adhesive composition and the adhesion performance to the polyethylene substrate were measured in the same manner as in Example 1. These are shown in Table 1 and Table 2, respectively.
- Example 3 The following raw materials were charged into a 2 L glass flask equipped with a thermometer, a condenser, and a stirring rod, and stirred at 80 ° C. for 1 hour to uniformly dissolve the resin component to prepare an adhesive composition.
- Kernel KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- YS Polystar U130 Yasuhara Chemical Co., Ltd. terpene phenol type tackifier
- 40 parts-MCH methylcyclohexane
- Example 4 The following raw materials were charged into a 2 L glass flask equipped with a thermometer, a condenser, and a stirring rod, and stirred at 80 ° C. for 1 hour to uniformly dissolve the resin component to prepare an adhesive composition.
- ⁇ Kernel KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- 90 parts ⁇ Hardlene DX-526P (chlorine content 26 wt%) (Toyobo Co., Ltd. chlorinated modified polypropylene copolymer) 10 parts ⁇ YS Polystar T130 (Yasuhara Chemical Co., Ltd.
- Example 5 The following raw materials were charged into a 2 L glass flask equipped with a thermometer, a condenser, and a stirring rod, and stirred at 80 ° C. for 1 hour to uniformly dissolve the resin component to prepare an adhesive composition.
- ⁇ Kernel KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- El Modu S400 Idemitsu Kosan Co., Ltd. polypropylene resin
- YS Polystar T130 Yasuhara Chemical Co., Ltd.
- Example 6 The following raw materials were charged into a 2 L glass flask equipped with a thermometer, a condenser, and a stirring rod, and stirred at 80 ° C. for 1 hour to uniformly dissolve the resin component to prepare an adhesive composition.
- ⁇ Kernel KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- Hardlene DX-526P chlorine content 26 wt%)
- Toyobo Co., Ltd. chlorinated modified polypropylene copolymer 10 parts
- Clearon K100 Yasuhara Chemical Co., Ltd.
- Example 7 The following raw materials were charged into a 2 L glass flask equipped with a thermometer, a condenser, and a stirring rod, and stirred at 80 ° C. for 1 hour to uniformly dissolve the resin component to prepare an adhesive composition.
- ⁇ Kernel KJ640T Nippon Polyethylene Co., Ltd. modified polyethylene copolymer
- YS Polystar T130 110 parts of terpene phenol tackifier manufactured by Yashara Chemical Co., Ltd. 780 parts of MCH (methylcyclohexane)
- MCH methylcyclohexane
- Example 1 “Kernel KJ640T” in Example 1 was changed to “Lexpearl (registered trademark) ET330H” (modified polyethylene resin, melting point: 86 ° C., manufactured by Nippon Polyethylene Co., Ltd.), and the solution properties of the resulting adhesive composition are shown in Table 1. It was shown to. Since the adhesive composition obtained as shown in Table 1 was in a solidified state at room temperature (25 ° C.), the base material could not be applied and the adhesive performance could not be evaluated.
- “Lexpearl (registered trademark) ET330H” modified polyethylene resin, melting point: 86 ° C., manufactured by Nippon Polyethylene Co., Ltd.
- Example 2 “Kernel KJ640T” of Example 1 was changed to “Lex Pearl ET720X” (modified polyethylene resin, melting point: 98 ° C., manufactured by Nippon Polyethylene Co., Ltd.), and Table 1 shows the solution properties of the obtained adhesive composition. Since the adhesive composition obtained as shown in Table 1 was in a solidified state at room temperature (25 ° C.), the base material could not be applied and the adhesive performance could not be evaluated.
- “Kernel KJ640T” of Example 1 was changed to “Lex Pearl ET720X” (modified polyethylene resin, melting point: 98 ° C., manufactured by Nippon Polyethylene Co., Ltd.)
- Table 1 shows the solution properties of the obtained adhesive composition. Since the adhesive composition obtained as shown in Table 1 was in a solidified state at room temperature (25 ° C.), the base material could not be applied and the adhesive performance could not be evaluated.
- Example 3 “Kernel KJ640T” in Example 1 was changed to “Nucleel (registered trademark) N1560” (modified polyethylene resin, melting point: 95 ° C., manufactured by Mitsui Chemicals, Inc.), and the solution properties of the resulting adhesive composition are shown in Table 1. Indicated. Since the adhesive composition obtained as shown in Table 1 was in a solidified state at room temperature (25 ° C.), the base material could not be applied and the adhesive performance could not be evaluated.
- Comparative Example 4 The following raw materials were charged into a 1 L glass flask equipped with a thermometer, a condenser, and a stirring rod, stirred at 80 ° C. for 1 hour, and the resin content was uniformly dissolved to prepare an adhesive composition.
- ⁇ Kernel KJ640T melting point: 58 ° C
- MCH methylcyclohexane
- Comparative Example 5 The following raw materials were charged into a 1 L glass flask equipped with a thermometer, a condenser, and a stirring rod, stirred at 80 ° C. for 1 hour, and the resin content was uniformly dissolved to prepare an adhesive composition.
- ⁇ Kernel KJ640T (melting point: 58 ° C) (Nippon Polyethylene Co., Ltd. modified polyethylene resin) 100 parts ⁇ YS Polystar T130 (Yasuhara Chemical Co., Ltd.
- Comparative Example 6 The following raw materials were charged into a 1 L glass flask equipped with a thermometer, a condenser, and a stirring rod, stirred at 80 ° C. for 1 hour, and the resin content was uniformly dissolved to prepare an adhesive composition.
- ⁇ Kernel KJ640T melting point: 58 ° C
- YS Polystar T130 Yasuhara Chemical Co., Ltd.
- Example 7 “YS Polystar T130” in Example 1 was changed to “YS Resin SX-100” (Yasuhara Chemical's styrene resin), and the solution properties of the resulting adhesive composition and the adhesive performance to a polyethylene substrate were the same as in Example 1. The results are shown in Tables 1 and 2, respectively.
- Comparative Example 8 “YS Polystar T130” in Example 1 was changed to “Halister TF” (Rosin-based resin manufactured by Harima Chemical Co., Ltd.), and the solution properties of the obtained adhesive composition and the adhesive performance to a polyethylene substrate were as in Example 1. Were measured in the same manner as shown in Tables 1 and 2, respectively.
- Example 9 “YS Polystar T130” in Example 1 was changed to “Haritack SE10” (rosin resin manufactured by Harima Chemicals Co., Ltd.), and the solution properties of the obtained adhesive composition and the adhesive performance to a polyethylene substrate were as in Example 1. Were measured in the same manner as shown in Tables 1 and 2, respectively.
- Example 10 The “YS Polystar T130” in Example 1 was changed to “Neotor (registered trademark) 125HK” (rosin resin manufactured by Harima Chemicals Co., Ltd.), and the solution properties of the resulting adhesive composition and the adhesive performance to polyethylene substrates Were measured in the same manner as in Example 1, and are shown in Tables 1 and 2, respectively.
- Comparative Example 11 “YS Polystar T130” in Example 1 was changed to “Super Ester A-75” (rosin resin manufactured by Arakawa Chemical Co., Ltd.), and the solution properties of the obtained adhesive composition and the adhesive performance to a polyethylene substrate were improved. Measurements were made in the same manner as in Example 1 and shown in Tables 1 and 2, respectively.
- Comparative Example 12 “YS Polystar T130” in Example 1 was changed to “Ester Gum H” (Rosin-based resin manufactured by Arakawa Chemical Co., Ltd.), and the solution properties of the obtained adhesive composition and the adhesive performance to a polyethylene substrate were examples. Measurements were made in the same manner as in Table 1, and are shown in Tables 1 and 2, respectively.
- Comparative Example 13 “YS Polystar T130” in Example 1 was changed to “Ester Gum AA-L” (rosin resin manufactured by Arakawa Chemical Co., Ltd.), and the solution properties of the obtained adhesive composition and the adhesive performance to a polyethylene substrate were improved. Measurements were made in the same manner as in Example 1 and shown in Tables 1 and 2, respectively.
- Example 14 “YS Polystar T130” in Example 1 was changed to “Arcon (registered trademark) P-90” (alicyclic saturated hydrocarbon resin manufactured by Arakawa Chemical Co., Ltd.), and the solution properties of the resulting adhesive composition And the adhesive performance with respect to a polyethylene base material was measured similarly to Example 1, and was shown in Table 1 and Table 2, respectively.
- Comparative Example 16 “YS Polystar T130” in Example 1 was changed to “Pine Crystal (registered trademark) KR-50M” (rosin metal salt resin manufactured by Arakawa Chemical Co., Ltd.), and solution properties of the resulting adhesive composition and polyethylene The adhesion performance to the substrate was measured in the same manner as in Example 1 and shown in Tables 1 and 2, respectively.
- the adhesive composition is excellent in stability at low temperatures and excellent in adhesion to each of a low density polyethylene (LDPE) substrate and a high density polyethylene (HDPE) substrate.
- LDPE low density polyethylene
- HDPE high density polyethylene
- Comparative Examples 1 to 3 are examples in which the melting point of the modified polyethylene copolymer (component A) exceeds 80 ° C.
- Comparative Examples 4 to 6 are 30 to 100 parts by weight of the B component with respect to 100 parts by weight of the A component.
- Examples in the case of deviating from the above and Comparative Examples 7 to 16 are examples in which a tackifier other than the terpene type is used as the B component.
- the adhesive composition of the present invention has good storage stability at low temperatures, excellent adhesion to polyolefin resin substrates, particularly polyethylene resin substrates, and coating, printing, adhesion, and coating on these substrates. It is useful for primer, paint, ink, coating agent and adhesive.
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Abstract
Description
本発明に用いる変性ポリエチレン共重合体(以下、単に「A成分」ともいう。)とは、エチレン-α-オレフィン共重合体、或いはアクリル酸、アクリル酸アルキルエステル、α,β-不飽和カルボン酸およびその酸無水物からなる群より選ばれる少なくとも1種とエチレンとの共重合体であることが好ましい。
本発明で使用される粘着付与剤(以下、単に「B成分」ともいう。)は変性ポリエチレン共重合体(A成分)に対して相溶性の高い事が必須の条件である。相溶性が悪い場合、本発明の接着剤組成物の特徴である低温下での有機溶剤溶液の安定性が得られないことがある。また種々ポリエチレン基材の内、特に高密度ポリエチレン(以下HDPEと示す)基材に対する接着性が発現されないことがある。ここでHDPE基材とは密度が0.94g/cm3以上のポリエチレン樹脂基材であり、特に0.95g/cm3付近のポリエチレン基材を意味するものである。
δ(高分子化合物)=ρΣE/M
ここでρ:高分子化合物の密度、M:高分子化合物の繰り返し構造単位の分子量、E:高分子化合物を構成する個々の構造単位のモル凝集エネルギー定数である。Eの数値は種々文献に掲載されている数値を使用する事が出来る。数値が記載されている文献としては例えば、J.Paint Technology vol.42 76-118 (1970)が挙げられる。
本発明の接着剤組成物に用いられる有機溶剤(以下、単に「C成分」ともいう。)としては、トルエン、キシレン等の芳香族炭化水素、シクロヘキサン、メチルシクロヘキサン等脂環族炭化水素の各々単独或いはこれらの混合物を主溶剤として用いることが出来る。また、n-ブチルアセテート、エチルアセテート、1-ブタノール、2-ブタノール、メチルエチルケトン、メチルイソブチルケトン等を全有機溶媒に対して、20重量%未満の範囲で上記主溶剤に混合して用いる事が出来る。
本発明の接着剤組成物には有機溶剤に対する溶解性をより高める目的で、ポリプロピレン系樹脂(以下、単に「D成分」ともいう)を配合することができる。ポリプロピレン系樹脂(D成分)としては、非結晶性ポリプロピレン樹脂や、塩素化変性ポリプロピレン共重合体を挙げることができる。塩素化変性ポリプロピレン共重合体は、ポリプロピレンまたはプロピレン-α-オレフィン共重合体の側鎖に塩素原子を付加させたものが好ましい。ここで、プロピレン-α-オレフィン共重合体とは、プロピレンを主体としてこれにα-オレフィンを共重合したものである。α-オレフィンとしては、例えば、エチレン、1-ブテン、1-ヘプテン、1-オクテン、4-メチル-1-ペンテンなどを1種または数種用いることができる。これらの中では、1-ブテンが好ましい。プロピレン-α-オレフィン共重合体のプロピレン成分とα-オレフィン成分との比率には特に制限はないが、プロピレン成分が50モル%以上であることが好ましく、50モル%超であることがより好ましい。市販されているこれら塩素化変性ポリプロピレン共重合体の具体例としては東洋紡(株)製ハードレン(登録商標)DXシリーズ(「DX-526P」、「DX-530P」等)が挙げられる。一方、非結晶性ポリプロピレン樹脂としては出光興産(株)製エルモーデュ(登録商標)(「エルモーデュS400」、「エルモーデュS600」、「エルモーデュS901」)等が挙げられる。
本発明の接着剤組成物は、前記融点が80℃未満の変性ポリエチレン共重合体(A成分)、テルペン系粘着付与剤(B成分)、および有機溶剤(C成分)を含有し、A成分100重量部に対して、B成分が30~100重量部の組成物である。或いは場合によりA成分100重量部に対して、15重量部未満のポリプロピレン系樹脂(D成分)をさらに含有する組成物である。
5cm径、深さ1cmのアルミ製カップにサンプル(接着剤組成物)約1gを採り、精秤する。次いでサンプルを入れたアルミカップを60℃の減圧乾燥機で6時間乾燥させる。減圧乾燥機から取り出したアルミカップをデシケーターに入れ、室温で30分放置・冷却する。デシケーターからアルミカップを取り出し、重量を精秤し、減圧乾燥前後の重量変化(下記式)からサンプル(接着剤組成物)の固形分濃度の重量%を算出する。
接着剤組成物の固形分濃度(重量%)=[(減圧乾燥前のサンプル重量)-(減圧乾燥後のサンプル重量)]/(減圧乾燥前のサンプル重量)×100
上記固形分濃度の測定で得られた乾燥したサンプル(樹脂)を重クロロホルムに溶解し、ヴァリアン社製核磁気共鳴分析計(NMR)“ジェミニ-400-MR”を用い、1H-NMR分析により変性ポリエチレン共重合体、粘着付与剤およびポリプロピレン系樹脂の比率を求めた。
実施例・比較例で得られた接着剤組成物を50CC密栓付ガラス製サンプル管に入れ25℃の恒温水槽で12時間保持した。次いで東機産業(株)製“Viscometer TV-22”(E型粘度計)を用い、0.6gのサンプルをローターNo.0.8°(=48’)×R24、レンジH、回転数5rpm、25℃の条件で測定した。
TAインストルメント社製DSC Q2000を用い、変性ポリエチレン共重合体サンプル約5mgを密閉式アルミパンに秤量し、10℃/min.の速度で-50℃→200℃→-50℃の昇温・冷却サイクルを2回繰り返した。2回目昇温時に現れた吸熱ピークの極小点温度を融点として読み取った。
実施例・比較例で調製された接着剤組成物を20℃及び15℃のインキュベーター内で静置状態で保存した。24時間放置後の溶液の外観変化を観察し、結果を以下の様な基準で評価した。
○:接着剤組成物が調製時と同等の流動性を保持している。
△:接着剤組成物が増粘しているが流動性は保持している。
×:接着剤組成物が固化しており、流動性が無い。
実施例・比較例で得られた接着剤組成物を(株)パルテック社製2mm厚、25mm×100mmサイズの高密度ポリエチレン(HDPE)テストピース(密度:0.95g/cm3)及び同サイズの同社製低密度ポリエチレン(LDPE)テストピース(密度:0.92g/cm3)に#16Eのワイヤーバーを用いて乾燥後の膜厚が10μmとなるように塗工し、90℃の熱風乾燥機で10分乾燥させた。乾燥機から取り出したテストピースを室温下で1時間放置した後、塗装面にカッターナイフにて1mm間隔で100個の碁盤目を作り、その上にセロハン粘着テープを使用して引き剥がし(碁盤目剥離試験)を実施した。剥がれたマス目を数え、全て剥がれた場合は、0/100とし、全く剥がれが生じなかった場合は、100/100とした。結果を表2に示した。
中川製袋加工(株)製の40μm厚LDPEフィルム(密度:0.92g/cm3)に#16Eのワイヤーバーを用いて実施例・比較例で得られた接着剤組成物を乾燥後の膜厚が10μmとなるように塗工し、90℃の熱風乾燥機で10分乾燥させた。乾燥後、フィルムから2.5cm×10cmの短冊状片を10枚切り出し、塗工面同士を貼り合せ、90℃、3kgf/cm2圧で30秒間ヒートシールし、1cm幅のヒートシール層を形成した試験片を5枚作製した。試験片の先端を引っ張り試験機(Orientec社製“RTM-100”)のチャックで挟み5kgfロードセルを用い、25℃雰囲気下、50mm/分の引っ張り速度で上下方向に引いて90°剥離試験を実施した。得られた5個の剥離強度の平均値を算出し、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した1Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネル(登録商標)KJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)100部
・YSポリスター(登録商標)T130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)50部
・MCH(メチルシクロヘキサン)850部
冷却後溶液を取り出し、接着剤組成物を得た。固形分濃度、変性ポリエチレン共重合体樹脂および粘着付与剤の含有量を測定し、その結果から上記各成分の重量比率を求めた。変性ポリエチレン共重合体の融点の測定値と共に表1に示した。併せて上述した評価測定方法に従い、25℃での溶液粘度、20℃及び15℃保存下での溶液(接着剤組成物)の保存安定性、及びHDPE及びLDPEシート碁盤目剥離とLDPEフィルム90°剥離試験の評価結果を表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した1Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・レクスパールET350X
(日本ポリエチレン(株)製変性ポリエチレン共重合体)100部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)70部
・トルエン 963部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した2Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)100部
・YSポリスターU130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)40部
・MCH(メチルシクロヘキサン)793部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した2Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)90部
・ハードレンDX-526P(塩素含有率26重量%)
(東洋紡(株)製塩素化変性ポリプロピレン共重合体)10部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)50部
・CH(シクロヘキサン)765部
・酢酸エチル85部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した2Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)90部
・エルモーデュS400
(出光興産(株)製ポリプロピレン樹脂)10部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)50部
・CH(シクロヘキサン)765部
・酢酸エチル85部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した2Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)100部
・ハードレンDX-526P(塩素含有率26重量%)
(東洋紡(株)製塩素化変性ポリプロピレン共重合体)10部
・クリアロンK100
(ヤスハラケミカル(株)製水添テルペン系粘着付与剤)50部
・CH(シクロヘキサン)765部
・酢酸ブチル85部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した2Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T
(日本ポリエチレン(株)製変性ポリエチレン共重合体)110部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)110部
・MCH(メチルシクロヘキサン)780部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「カーネルKJ640T」を「レクスパール(登録商標)ET330H」(日本ポリエチレン(株)製変性ポリエチレン樹脂 融点:86℃)に変更し、得られた接着剤組成物の溶液特性を表1に示した。表1に示したとおり得られた接着剤組成物は室温下(25℃)では固化した状態であったため、基材塗布が不可能で接着性能を評価する事が出来なかった。
実施例1の「カーネルKJ640T」を「レクスパールET720X」(日本ポリエチレン(株)製変性ポリエチレン樹脂 融点:98℃)に変更し、得られた接着剤組成物の溶液特性を表1に示した。表1に示したとおり得られた接着剤組成物は室温下(25℃)では固化した状態であったため、基材塗布が不可能で接着性能を評価する事が出来なかった。
実施例1の「カーネルKJ640T」を「ニュクレル(登録商標)N1560」(三井化学(株)製変性ポリエチレン樹脂 融点:95℃)に変更し、得られた接着剤組成物の溶液特性を表1に示した。表1に示したとおり得られた接着剤組成物は室温下(25℃)では固化した状態であったため、基材塗布が不可能で接着性能を評価する事が出来なかった。
以下の原料を温度計、コンデンサー、攪拌棒を具備した1Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T(融点:58℃)
(日本ポリエチレン(株)製変性ポリエチレン樹脂)150部
・MCH(メチルシクロヘキサン) 850部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した1Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T(融点:58℃)
(日本ポリエチレン(株)製変性ポリエチレン樹脂)100部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)20部
・MCH(メチルシクロヘキサン)680部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
以下の原料を温度計、コンデンサー、攪拌棒を具備した1Lガラスフラスコに仕込み、80℃で1時間攪拌し、樹脂分を均一溶解して接着剤組成物を調製した。
・カーネルKJ640T(融点:58℃)
(日本ポリエチレン(株)製変性ポリエチレン樹脂)100部
・YSポリスターT130
(ヤスハラケミカル(株)製テルペンフェノール系粘着付与剤)120部
・MCH(メチルシクロヘキサン)1247部
冷却後溶液を取り出し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「YSレジンSX-100」(ヤスハラケミカル製スチレン樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「ハリスターTF」(ハリマ化成(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「ハリタックSE10」(ハリマ化成(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「ネオトール(登録商標)125HK」(ハリマ化成(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「スーパーエステルA-75」(荒川化学(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「エステルガムH」(荒川化学(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「エステルガムAA-L」(荒川化学(株)製ロジン系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「アルコン(登録商標)P-90」(荒川化学(株)製脂環族飽和炭化水素系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「アルコンM-90」(荒川化学(株)製脂環族飽和炭化水素系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
実施例1の「YSポリスターT130」を「パインクリスタル(登録商標)KR-50M」(荒川化学(株)製ロジン金属塩系樹脂)に変更し、得られた接着剤組成物の溶液特性及びポリエチレン基材に対する接着性能を実施例1と同様に測定し、各々表1、表2に示した。
尚、比較例1~3は変性ポリエチレン共重合体(A成分)の融点が80℃を超える場合の例、比較例4~6はA成分100重量部に対してB成分が30~100重量部を外れる場合の例、及び比較例7~16はB成分としてテルペン系以外の粘着付与剤を使用した場合の例である。
Claims (5)
- 融点が80℃未満の変性ポリエチレン共重合体(A成分)、テルペン系粘着付与剤(B成分)、および有機溶剤(C成分)を含有し、A成分100重量部に対して、B成分が30~100重量部である接着剤組成物。
- テルペン系粘着付与剤(B成分)が、テルペンフェノール樹脂である事を特徴とする請求項1に記載の接着剤組成物。
- 有機溶剤(C成分)が、脂環族炭化水素化合物および/または芳香族炭化水素化合物である事を特徴とする請求項1または2に記載の接着剤組成物。
- 前記A成分、B成分およびC成分の合計重量に占めるA成分とB成分の重量比率が20重量%以下である請求項1~3のいずれかに記載の接着剤組成物。
- さらにポリプロピレン系樹脂(D成分)を含有し、D成分が前記A成分100重量部に対して15重量部未満である事を特徴とする請求項1~3のいずれかに記載の接着剤組成物。
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WO2023136162A1 (ja) * | 2022-01-14 | 2023-07-20 | Eneos株式会社 | ポリマー組成物 |
JP7540443B2 (ja) | 2019-09-19 | 2024-08-27 | 東洋紡エムシー株式会社 | ポリオレフィン系塗料組成物 |
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US20190048235A1 (en) | 2019-02-14 |
KR102461571B1 (ko) | 2022-10-31 |
EP3415581B8 (en) | 2022-04-13 |
EP3415581A1 (en) | 2018-12-19 |
EP3415581A4 (en) | 2019-08-14 |
TW201802210A (zh) | 2018-01-16 |
TWI710612B (zh) | 2020-11-21 |
KR20180107244A (ko) | 2018-10-01 |
US10731060B2 (en) | 2020-08-04 |
CN108699412B (zh) | 2021-04-27 |
CN108699412A (zh) | 2018-10-23 |
JP6794999B2 (ja) | 2020-12-02 |
JPWO2017138399A1 (ja) | 2018-12-06 |
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