WO2014136940A1 - Hot-melt-adhesive composition - Google Patents
Hot-melt-adhesive composition Download PDFInfo
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- WO2014136940A1 WO2014136940A1 PCT/JP2014/055975 JP2014055975W WO2014136940A1 WO 2014136940 A1 WO2014136940 A1 WO 2014136940A1 JP 2014055975 W JP2014055975 W JP 2014055975W WO 2014136940 A1 WO2014136940 A1 WO 2014136940A1
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- styrene
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- block copolymer
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- butadiene
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
Definitions
- the present invention relates to a hot melt adhesive composition.
- One-component moisture-curing urethane-based hot melt adhesives based on urethane prepolymers with an isocyanate group in the molecule are applied to the adherend in a molten state, and are cooled, also called reactive hot melt adhesives. After solidifying, the reaction of the isocyanate group proceeds by the moisture present in the adherend or air to form a crosslinked structure and harden. Therefore, in the one-component moisture-curing urethane hot melt adhesive, higher heat resistance is expressed as compared to other hot melt adhesives due to the molecular growth reaction of the urethane prepolymer (see, for example, Patent Documents 1 and 2). .)
- thermo stability the property stability in the molten state
- a foreign substance in which a part of the component was gelled might be mixed.
- the peel strength at 120 ° C. was low and the heat resistance was not sufficient depending on the kind of the adherend.
- an object of the present invention is to provide a hot melt adhesive composition having excellent thermal stability and good heat resistance.
- the present inventors have blended a specific amount of a nitrone derivative with a predetermined styrene-butadiene block copolymer, thereby providing excellent thermal stability and good heat resistance. It discovered that it became a hot-melt-adhesive composition, and completed this invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
- the styrene-butadiene block copolymer is a styrene-butadiene-styrene block copolymer (SBS) and / or a styrene-butadiene-butylene-styrene block copolymer (SBBS),
- SBS styrene-butadiene-styrene block copolymer
- SBBS styrene-butadiene-butylene-styrene block copolymer
- the hot melt adhesive composition of the present invention contains a styrene-butadiene block copolymer and a nitrone derivative, and the styrene-butadiene block copolymer described above.
- styrene-butadiene-styrene block copolymer SBS
- SBBS styrene-butadiene-butylene-styrene block copolymer
- the hot melt adhesive composition is 1 to 10 parts by mass with respect to 100 parts by mass.
- a hot melt adhesive composition having excellent thermal stability and good heat resistance is obtained.
- cyclization occurs between part or all of the nitrone derivative and the butadiene double bond of the styrene-butadiene block copolymer in the molten state at the time of kneading or use. It is considered that the interaction (intermolecular force) between the styrene-butadiene block copolymers is increased by the occurrence of the addition reaction (see the following formulas (I) and (II)).
- a composition prepared without blending the nitrone derivative has a low melt viscosity at 120 ° C., as shown in Comparative Examples described later.
- the nitrone derivative and the styrene-butadiene block copolymer are kneaded at a temperature (for example, about 160 to 180 ° C.) assuming a molten state at the time of use, and then the resulting mixture is mixed with cyclohexane, ethyl acetate, or the like.
- the styrene-butadiene block copolymer contained in the adhesive composition of the present invention is a styrene-butadiene-styrene block copolymer (SBS) and / or a styrene-butadiene-butylene-styrene block copolymer (SBBS). is there.
- SBS styrene-butadiene-styrene block copolymer
- SBBS styrene-butadiene-butylene-styrene block copolymer
- the styrene content of the styrene-butadiene block copolymer is not particularly limited, but for SBS, the mass ratio of styrene to butadiene (styrene / butadiene) is preferably 20/80 to 50/50. More preferably, the amount is 30/70 to 45/55.
- the melt flow rate (MFR: 200 ° C., load 5.0 kg) of the styrene-butadiene block copolymer is not particularly limited, but is preferably 100 or less, more preferably 2 to 80.
- SBS Asaprene (registered trademark) A, 125 and 126S manufactured by Asahi Kasei Chemicals, Asaprene (registered trademark) T-411, T-432, T-
- SBS Asaprene (registered trademark) A, 125 and 126S manufactured by Asahi Kasei Chemicals
- Commercially available products such as 437, T-438 and T-439 can be used, and commercially available products such as Tuftec (registered trademark) P1000, P1500 and P2000 manufactured by the same company can be used as the SBBS.
- other styrene-butadiene block copolymers include, for example, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene-styrene block copolymer A combination (SEPS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), or the like can be used in combination.
- SEBS styrene-isoprene-styrene block copolymer
- SEBS styrene-ethylene-propylene-styrene block copolymer
- SEEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
- SEEPS styrene-ethylene-ethylene-propylene-styrene block
- the nitrone derivative contained in the adhesive composition of the present invention is not particularly limited as long as it is a compound in which an oxygen atom is bonded to a nitrogen atom of a Schiff base.
- the nitrone derivative is a nitrone having an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, because both the thermal stability and the heat resistance are improved. It is preferable that there is, for example, a nitrone represented by the following formula (a).
- X and Y each independently represent an aliphatic or aromatic hydrocarbon group which may have a substituent, and at least one of X or Y has a substituent. Or an aromatic hydrocarbon group or an aromatic heterocyclic group.
- Examples of the aliphatic hydrocarbon group represented by X and Y include an alkyl group, a cycloalkyl group, and an alkenyl group.
- Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, Examples thereof include a tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, n-hexyl group, n-heptyl group, and n-octyl group.
- Alkyl groups having 1 to 6 carbon atoms are more preferable.
- the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Among them, a cycloalkyl group having 3 to 10 carbon atoms is preferable, and a cycloalkyl group having 3 to 6 carbon atoms is preferable. More preferred.
- Examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, and a 2-butenyl group. Among them, an alkenyl group having 2 to 18 carbon atoms is preferable. An alkenyl group having 2 to 6 carbon atoms is more preferable.
- Examples of the aromatic hydrocarbon group represented by X and Y include an aryl group and an aralkyl group.
- the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Among them, an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. A phenyl group and a naphthyl group are more preferable.
- Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group. Among them, an aralkyl group having 7 to 13 carbon atoms is preferable, an aralkyl group having 7 to 11 carbon atoms is more preferable, and a benzyl group is preferable. Further preferred.
- Examples of the aromatic heterocyclic group represented by X and Y include pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl (imidazole), oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl (pyridine). Group), furan group, thiophene group, pyridazinyl group, pyrimidinyl group, pyrazinyl group and the like. Of these, a pyridyl group is preferable.
- the substituent that the hydrocarbon group represented by X and Y may have is not particularly limited, and examples thereof include a lower alkyl group having 1 to 4 carbon atoms, a hydroxy group, an amino group, a nitro group, a carbonyl group, and a carboxy group. Group, carbonate group, urethane group, sulfonyl group, alkoxy group, ester group, halogen atom and the like.
- the aromatic hydrocarbon group having such a substituent include an aryl group having a substituent such as a tolyl group and a xylyl group; and a substituent such as a methylbenzyl group, an ethylbenzyl group, and a methylphenethyl group.
- the nitrone represented by the formula (a) is an aromatic hydrocarbon group or an aromatic heterocyclic group in which at least one of X and Y in the formula (a) may have a substituent.
- both X and Y are preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
- the above nitrone derivative has better thermal stability and can improve intermolecular force, so that the nitrone having an aromatic hydrocarbon group or aromatic heterocyclic group having a carboxy group as a substituent (hereinafter referred to as “nitrone”)
- nitrone aromatic hydrocarbon group or aromatic heterocyclic group having a carboxy group as a substituent
- carboxy nitrone For convenience, it is also referred to as “carboxy nitrone”
- examples thereof include nitrones represented by the following formula (b).
- m and n each independently represent an integer of 0 to 5, and the sum of m and n is 1 or more.
- the integer represented by m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing nitrone is improved and the synthesis is facilitated.
- the integer represented by n is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing nitrone is improved and the synthesis is facilitated.
- the total of m and n (m + n) is preferably 1 to 4 and more preferably 1 to 2 because the solubility in the polymer is good and the reactivity is excellent.
- the nitrone derivatives exemplified above may be used alone or in combination of two or more.
- the above carboxynitrone and an aromatic hydrocarbon group or aromatic heterocyclic group which may have a functional group (excluding the carboxy group) for the reason that the heat resistance becomes better and the economy is also excellent. It is preferable to use in combination with a nitrone having a nitrogen atom (for example, diphenylnitrone).
- the content of the nitrone derivative is 1 to 10 parts by mass with respect to 100 parts by mass of the styrene-butadiene block copolymer.
- the amount is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the coalescence.
- the method for synthesizing the nitrone derivative is not particularly limited, and a conventionally known method can be used.
- a compound having a hydroxyamino group (—NHOH) and a compound having an aldehyde group (—CHO) are mixed in an organic solvent (eg, methanol, ethanol) at a molar ratio of 1.5: 1 to 1: 1.5. , Tetrahydrofuran, etc.) at room temperature for 1 to 24 hours to react both groups to give a nitrone having a nitrone group represented by the formula “—N + (—O ⁇ ) ⁇ CH—”.
- the adhesive composition of the present invention may further contain an additive as necessary within the range not impairing the object and effect of the present invention, in addition to the above-described styrene-butadiene block copolymer and nitrone derivative.
- additives examples include diene rubbers and non-diene rubbers other than the styrene-butadiene block copolymer, thermoplastic elastomers, catalysts, fillers, plasticizers, softeners, adhesion promoters, tackifiers, waxes, Examples include vulcanization accelerators, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, stabilizers, fragrances, thixotropic agents, ultraviolet absorbers, and silane coupling agents.
- the filler examples include calcium carbonate, talc, white carbon, silica, and carbon black.
- silica when silica is used as a filler, the content thereof is 5 parts by mass or less with respect to 100 parts by mass of the styrene-butadiene block copolymer, because the heat resistance becomes better. Preferably, it is 4 parts by mass or less.
- plasticizer examples include paraffinic, naphthenic or aromatic process oils; liquid resins such as liquid polybutene, liquid polybutadiene or liquid polyisoprene; liquid paraffin; olefin process oil; Can be mentioned.
- Examples of the tackifier include rosin resin, terpene resin, petroleum resin, coumarone-indene resin and the like, modified products thereof, and hydrogenated products.
- examples of petroleum resins include aliphatic, alicyclic and aromatic resins made from petroleum. Specifically, C5 petroleum resins, C9 petroleum resins, and copolymer petroleum resins. Suitable examples include alicyclic saturated hydrocarbon resins and styrene petroleum resins.
- anti-aging agent examples include hindered phenol compounds and hindered amine compounds.
- the method for producing the adhesive composition of the present invention is not particularly limited, and examples thereof include a method of kneading each of the above-described components using a known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.). It is done.
- a known method and apparatus for example, a Banbury mixer, a kneader, a roll, etc.
- the ratio of the melt viscosity at 120 ° C. to the melt viscosity at 180 ° C. is preferably 7 or more, more preferably 8 or more.
- the adhesive material composition of the present invention preferably has a melt viscosity at 180 ° C. of 4000 mPas or less, and more preferably 3000 mPas or less.
- members (adhered bodies) that can use the adhesive composition of the present invention include glass; various metals such as aluminum, anodized aluminum, iron, steel plate, galvanized steel plate, copper, and stainless steel; mortar and Porous members such as stone materials; members coated by fluorine electrodeposition, acrylic electrodeposition, fluorine coating, urethane coating, acrylic urethane coating; such as silicone, modified silicone, urethane, polysulfide, and polyisobutylene Cured products of sealing materials; polyolefins such as polyethylene, resins such as vinyl chloride resins and acrylic resins; rubbers such as NBR and EPDM.
- various metals such as aluminum, anodized aluminum, iron, steel plate, galvanized steel plate, copper, and stainless steel
- mortar and Porous members such as stone materials
- members coated by fluorine electrodeposition, acrylic electrodeposition, fluorine coating, urethane coating, acrylic urethane coating such as silicone, modified silicone, urethane, polysulfide, and polyis
- Examples 1 to 13 The components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 below. Specifically, first, a styrene-butadiene block copolymer and a plasticizer are added to a glass container whose temperature in the container is set to 160 ° C., kneaded for 5 minutes, then a nitrone derivative is added, and further 10 minutes. Kneaded. Next, the temperature in the glass container was set to 130 ° C., a filler and a tackifier were added, kneaded for 10 minutes, an anti-aging agent was added, and the mixture was further kneaded for 5 minutes. Thereafter, the mixture was taken out and cooled to prepare a hot melt adhesive composition.
- Example 14 The components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 below. Specifically, a hot melt adhesive composition was prepared in the same manner as in Example 1 except that the temperature in the glass container when kneading the styrene-butadiene block copolymer was 130 ° C. .
- melt viscosity and melt viscosity ratio The melt viscosity (mPas) at 120 ° C., 140 ° C., 160 ° C. and 180 ° C. of each hot melt adhesive composition was measured using a single cylindrical rotational viscometer. Moreover, the ratio (120 degreeC viscosity / 180 degreeC viscosity) of the melt viscosity in 120 degreeC and the melt viscosity in 180 degreeC was computed from the measurement result.
- Softening point The softening point (° C.) of each hot melt adhesive composition was measured by a ring method using a glycerin bath based on JIS K6863: 1994.
- thermo stability Each hot melt adhesive composition was allowed to stand for 72 hours in a melted state at 180 ° C. The presence or absence of foreign matter (gelled product) after 72 hours was confirmed. If there is no foreign material, it can be evaluated that the thermal stability is excellent, and if there is a foreign material, it can be evaluated that the thermal stability is poor.
- Example 1 and Example 14 were washed with cyclohexane to isolate only the polymer, and then 1 H-NMR (proton nuclear magnetic resonance) measurement was performed.
- the polymer derived from the hot melt adhesive composition prepared in Example 1 had a proton chemical shift associated with the disappearance of butadiene (double bond) in the styrene-butadiene block copolymer. It was confirmed that a cycloaddition reaction (see the above formula (I)) occurred between a part of the nitrone derivative and the butadiene double bond of the styrene-butadiene block copolymer.
- SBS1 Asaprene T-439 (styrene / butadiene mass ratio: 45/55, manufactured by Asahi Kasei Chemicals Corporation)
- SBS2 Asaprene T-432 (styrene / butadiene mass ratio: 30/70, manufactured by Asahi Kasei Chemicals)
- SBBS Tuftec P1000 (styrene / butadiene mass ratio: 30/70, manufactured by Asahi Kasei Chemicals Corporation)
- Nitron derivative Carboxynitrone, pyridylnitrone, diphenylnitrone synthesized by the above-described method was used.
- the hot melt adhesive compositions of Examples 1 to 14 prepared by blending a specific amount of a nitrone derivative with a predetermined styrene-butadiene block copolymer are excellent in thermal stability and peel at 120 ° C. It was found that the strength (heat resistance) was also good. In particular, when Example 1 and Comparative Example 1 are compared, the melt viscosity at 120 ° C. rises almost twice due to the presence or absence of the nitrone derivative, and the melt viscosity at 180 ° C. becomes comparable, and the nitrone derivative is added. Thus, it can be seen that not only the thermal stability and heat resistance, but also the workability at the time of coating has been remarkably improved.
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Abstract
Description
そのため、一液湿気硬化型ウレタン系ホットメルト接着剤では、ウレタンプレポリマーの分子成長反応により、他のホットメルト接着剤に比べて、高い耐熱性が発現される(例えば、特許文献1および2参照。)。 One-component moisture-curing urethane-based hot melt adhesives based on urethane prepolymers with an isocyanate group in the molecule are applied to the adherend in a molten state, and are cooled, also called reactive hot melt adhesives. After solidifying, the reaction of the isocyanate group proceeds by the moisture present in the adherend or air to form a crosslinked structure and harden.
Therefore, in the one-component moisture-curing urethane hot melt adhesive, higher heat resistance is expressed as compared to other hot melt adhesives due to the molecular growth reaction of the urethane prepolymer (see, for example, Patent Documents 1 and 2). .)
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have blended a specific amount of a nitrone derivative with a predetermined styrene-butadiene block copolymer, thereby providing excellent thermal stability and good heat resistance. It discovered that it became a hot-melt-adhesive composition, and completed this invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
上記スチレン-ブタジエンブロック共重合体が、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、および/または、スチレン-ブタジエン-ブチレン-スチレンブロック共重合体(SBBS)であり、
上記ニトロン誘導体の含有量が、上記スチレン-ブタジエンブロック共重合体100質量部に対して1~10質量部である、ホットメルト接着剤組成物。
(2)120℃における溶融粘度と180℃における溶融粘度との比率(120℃粘度/180℃粘度)が7以上である、上記(1)に記載のホットメルト接着剤組成物。
(3)180℃における溶融粘度が4000mPas以下である、上記(2)に記載のホットメルト接着剤組成物。
(4)上記ニトロン誘導体が、置換基を有していてもよい芳香族炭化水素基または芳香族複素環基を有するニトロンである、上記(1)~(3)のいずれかに記載のホットメルト接着剤組成物。
(5)上記ニトロン誘導体が、上記置換基としてカルボキシ基を有する上記(4)に記載のホットメルト接着剤組成物。
(6)シリカの含有量が、上記スチレン-ブタジエンブロック共重合体100質量部に対して5質量部以下である、上記(1)~(5)のいずれかに記載のホットメルト接着剤組成物。 (1) containing a styrene-butadiene block copolymer and a nitrone derivative;
The styrene-butadiene block copolymer is a styrene-butadiene-styrene block copolymer (SBS) and / or a styrene-butadiene-butylene-styrene block copolymer (SBBS),
A hot melt adhesive composition, wherein the content of the nitrone derivative is 1 to 10 parts by mass with respect to 100 parts by mass of the styrene-butadiene block copolymer.
(2) The hot melt adhesive composition according to (1), wherein the ratio of the melt viscosity at 120 ° C. to the melt viscosity at 180 ° C. (120 ° C. viscosity / 180 ° C. viscosity) is 7 or more.
(3) The hot melt adhesive composition according to (2), wherein the melt viscosity at 180 ° C. is 4000 mPas or less.
(4) The hot melt according to any one of (1) to (3), wherein the nitrone derivative is an nitrone having an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. Adhesive composition.
(5) The hot melt adhesive composition according to (4), wherein the nitrone derivative has a carboxy group as the substituent.
(6) The hot melt adhesive composition according to any one of (1) to (5), wherein the silica content is 5 parts by mass or less based on 100 parts by mass of the styrene-butadiene block copolymer. .
これは、詳細には明らかではないが、混練時または使用時の溶融状態において、上記ニトロン誘導体の一部または全部と上記スチレン-ブタジエンブロック共重合体のブタジエンの二重結合との間に環化付加反応(下記式(I)および(II)参照)が生起することにより、上記スチレン-ブタジエンブロック共重合体同士の相互作用(分子間力)が高まったためと考えられる。このことは後述する比較例に示すように、上記ニトロン誘導体を配合せずに調製した組成物では、120℃における溶融粘度が低いという事実からも推察することができる。
なお、使用時の溶融状態を想定した温度(例えば、160~180℃程度)で上記ニトロン誘導体と上記スチレン-ブタジエンブロック共重合体とを混練させた後、得られた混合物をシクロヘキサンや酢酸エチル等で洗浄した後に、1H-NMR(プロトン核磁気共鳴)測定を行うと、上記スチレン-ブタジエンブロック共重合体のブタジエン(二重結合)の消失に伴うプロトンのケミカルシフトにより、上記環化付加反応が生起していることを確認することができる。 In the present invention, as described above, by adding a specific amount of a nitrone derivative to a predetermined styrene-butadiene block copolymer, a hot melt adhesive composition having excellent thermal stability and good heat resistance is obtained. .
Although this is not clear in detail, cyclization occurs between part or all of the nitrone derivative and the butadiene double bond of the styrene-butadiene block copolymer in the molten state at the time of kneading or use. It is considered that the interaction (intermolecular force) between the styrene-butadiene block copolymers is increased by the occurrence of the addition reaction (see the following formulas (I) and (II)). This can also be inferred from the fact that a composition prepared without blending the nitrone derivative has a low melt viscosity at 120 ° C., as shown in Comparative Examples described later.
The nitrone derivative and the styrene-butadiene block copolymer are kneaded at a temperature (for example, about 160 to 180 ° C.) assuming a molten state at the time of use, and then the resulting mixture is mixed with cyclohexane, ethyl acetate, or the like. After 1 H-NMR (proton nuclear magnetic resonance) measurement, the cycloaddition reaction was caused by a chemical shift of protons accompanying the disappearance of butadiene (double bond) in the styrene-butadiene block copolymer. Can be confirmed.
本発明の接着剤組成物が含有する上記スチレン-ブタジエンブロック共重合体は、スチレン-ブタジエン-スチレンブロック共重合体(SBS)および/またはスチレン-ブタジエン-ブチレン-スチレンブロック共重合体(SBBS)である。 <Styrene-butadiene block copolymer>
The styrene-butadiene block copolymer contained in the adhesive composition of the present invention is a styrene-butadiene-styrene block copolymer (SBS) and / or a styrene-butadiene-butylene-styrene block copolymer (SBBS). is there.
同様に、上記スチレン-ブタジエンブロック共重合体のメルトフローレート(MFR:200℃、荷重5.0kg)は特に限定されないが、100以下であるのが好ましく、2~80であるのがより好ましい。 The styrene content of the styrene-butadiene block copolymer is not particularly limited, but for SBS, the mass ratio of styrene to butadiene (styrene / butadiene) is preferably 20/80 to 50/50. More preferably, the amount is 30/70 to 45/55.
Similarly, the melt flow rate (MFR: 200 ° C., load 5.0 kg) of the styrene-butadiene block copolymer is not particularly limited, but is preferably 100 or less, more preferably 2 to 80.
これらのうち、熱安定性がより良好となる理由から、SEBSを併用するのが好ましい。 In the present invention, in addition to SBS and / or SBBS, other styrene-butadiene block copolymers include, for example, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene-styrene block copolymer A combination (SEPS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), or the like can be used in combination.
Among these, it is preferable to use SEBS in combination for the reason that the thermal stability becomes better.
本発明の接着剤組成物が含有する上記ニトロン誘導体は、酸素原子がシッフ塩基の窒素原子に結合した化合物であれば特に限定されない。 <Nitron derivative>
The nitrone derivative contained in the adhesive composition of the present invention is not particularly limited as long as it is a compound in which an oxygen atom is bonded to a nitrogen atom of a Schiff base.
アリール基としては、例えば、フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基などが挙げられ、なかでも、炭素数6~14のアリール基が好ましく、炭素数6~10のアリール基がより好ましく、フェニル基、ナフチル基がさらに好ましい。
アラルキル基としては、例えば、ベンジル基、フェネチル基、フェニルプロピル基などが挙げられ、なかでも、炭素数7~13のアラルキル基が好ましく、炭素数7~11のアラルキル基がより好ましく、ベンジル基がさらに好ましい。 Examples of the aromatic hydrocarbon group represented by X and Y include an aryl group and an aralkyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Among them, an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. A phenyl group and a naphthyl group are more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group. Among them, an aralkyl group having 7 to 13 carbon atoms is preferable, an aralkyl group having 7 to 11 carbon atoms is more preferable, and a benzyl group is preferable. Further preferred.
なお、このような置換基を有する芳香族炭化水素基としては、例えば、トリル基、キシリル基などの置換基を有するアリール基;メチルベンジル基、エチルベンジル基、メチルフェネチル基などの置換基を有するアラルキル基;等が挙げられる。 The substituent that the hydrocarbon group represented by X and Y may have is not particularly limited, and examples thereof include a lower alkyl group having 1 to 4 carbon atoms, a hydroxy group, an amino group, a nitro group, a carbonyl group, and a carboxy group. Group, carbonate group, urethane group, sulfonyl group, alkoxy group, ester group, halogen atom and the like.
Examples of the aromatic hydrocarbon group having such a substituent include an aryl group having a substituent such as a tolyl group and a xylyl group; and a substituent such as a methylbenzyl group, an ethylbenzyl group, and a methylphenethyl group. An aralkyl group; and the like.
mが示す整数としては、ニトロンを合成する際の溶媒への溶解度が良好になり合成が容易になるという理由から、0~2の整数が好ましく、0~1の整数がより好ましい。
nが示す整数としては、ニトロンを合成する際の溶媒への溶解度が良好になり合成が容易になるという理由から、0~2の整数が好ましく、0~1の整数がより好ましい。
また、mとnとの合計(m+n)は、ポリマーへの溶解度が良好になり反応性が優れるという理由から、1~4が好ましく、1~2がより好ましい。 In the formula (b), m and n each independently represent an integer of 0 to 5, and the sum of m and n is 1 or more.
The integer represented by m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing nitrone is improved and the synthesis is facilitated.
The integer represented by n is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing nitrone is improved and the synthesis is facilitated.
The total of m and n (m + n) is preferably 1 to 4 and more preferably 1 to 2 because the solubility in the polymer is good and the reactivity is excellent.
特に、耐熱性がより良好となり、また、経済性にも優れる理由から、上記カルボキシニトロンと、官能基(カルボキシ基を除く)を有していてもよい芳香族炭化水素基または芳香族複素環基を有するニトロン(例えば、ジフェニルニトロン等)とを併用するのが好ましい。 In the present invention, the nitrone derivatives exemplified above may be used alone or in combination of two or more.
In particular, the above carboxynitrone and an aromatic hydrocarbon group or aromatic heterocyclic group which may have a functional group (excluding the carboxy group) for the reason that the heat resistance becomes better and the economy is also excellent. It is preferable to use in combination with a nitrone having a nitrogen atom (for example, diphenylnitrone).
上記ニトロン誘導体の合成方法は特に限定されず、従来公知の方法を用いることができる。例えば、ヒドロキシアミノ基(-NHOH)を有する化合物と、アルデヒド基(-CHO)を有する化合物とを、1.5:1~1:1.5のモル比で、有機溶媒(例えば、メタノール、エタノール、テトラヒドロフラン等)下で、室温で1~24時間撹拌することにより、両基が反応し、式「-N+(-O-)=CH-」で表されるニトロン基を有するニトロンを与える。 (Method for synthesizing nitrone derivatives)
The method for synthesizing the nitrone derivative is not particularly limited, and a conventionally known method can be used. For example, a compound having a hydroxyamino group (—NHOH) and a compound having an aldehyde group (—CHO) are mixed in an organic solvent (eg, methanol, ethanol) at a molar ratio of 1.5: 1 to 1: 1.5. , Tetrahydrofuran, etc.) at room temperature for 1 to 24 hours to react both groups to give a nitrone having a nitrone group represented by the formula “—N + (—O − ) ═CH—”.
本発明の接着剤組成物は、上述したスチレン-ブタジエンブロック共重合体およびニトロン誘導体以外に、本発明の目的および効果を損なわない範囲で、必要に応じてさらに添加剤を含有することができる。
添加剤としては、例えば、上記スチレン-ブタジエンブロック共重合体以外のジエン系ゴムおよび非ジエン系ゴム、熱可塑性エラストマー、触媒、充填剤、可塑剤、軟化剤、接着付与剤、タッキファイヤー、ワックス、加硫促進剤、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、安定剤、香料、揺変剤、紫外線吸収剤、シランカップリング剤等が挙げられる。 <Additives>
The adhesive composition of the present invention may further contain an additive as necessary within the range not impairing the object and effect of the present invention, in addition to the above-described styrene-butadiene block copolymer and nitrone derivative.
Examples of the additives include diene rubbers and non-diene rubbers other than the styrene-butadiene block copolymer, thermoplastic elastomers, catalysts, fillers, plasticizers, softeners, adhesion promoters, tackifiers, waxes, Examples include vulcanization accelerators, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, stabilizers, fragrances, thixotropic agents, ultraviolet absorbers, and silane coupling agents.
本発明においては、充填剤としてシリカを用いる場合、耐熱性がより良好となる理由から、その含有量は、上記スチレン-ブタジエンブロック共重合体100質量部に対して5質量部以下であるのが好ましく、4質量部以下であるのがより好ましい。 Among the above additives, specific examples of the filler include calcium carbonate, talc, white carbon, silica, and carbon black.
In the present invention, when silica is used as a filler, the content thereof is 5 parts by mass or less with respect to 100 parts by mass of the styrene-butadiene block copolymer, because the heat resistance becomes better. Preferably, it is 4 parts by mass or less.
これらのうち、石油樹脂としては、石油を原料とした脂肪族、脂環族、芳香族系の樹脂が挙げられ、具体的には、C5系石油樹脂、C9系石油樹脂、共重合系石油樹脂、脂環族飽和炭化水素樹脂、スチレン系石油樹脂等が好適に例示される。 Examples of the tackifier include rosin resin, terpene resin, petroleum resin, coumarone-indene resin and the like, modified products thereof, and hydrogenated products.
Among these, examples of petroleum resins include aliphatic, alicyclic and aromatic resins made from petroleum. Specifically, C5 petroleum resins, C9 petroleum resins, and copolymer petroleum resins. Suitable examples include alicyclic saturated hydrocarbon resins and styrene petroleum resins.
同様に、本発明の接着剤材組成物は、180℃における溶融粘度が4000mPas以下であるのが好ましく、3000mPas以下であるのがより好ましい。
溶融粘度および180℃粘度が上述した範囲内であると、本発明の接着剤組成物を被着体に適用(例えば、塗布など)する際の作業性が良好となり、120℃における剥離強度がより高くなり、耐熱性がより良好となる。 In the adhesive material composition of the present invention, the ratio of the melt viscosity at 120 ° C. to the melt viscosity at 180 ° C. (120 ° C. viscosity / 180 ° C. viscosity) is preferably 7 or more, more preferably 8 or more. .
Similarly, the adhesive material composition of the present invention preferably has a melt viscosity at 180 ° C. of 4000 mPas or less, and more preferably 3000 mPas or less.
When the melt viscosity and the 180 ° C. viscosity are within the above-described ranges, the workability when the adhesive composition of the present invention is applied to an adherend (for example, coating) is improved, and the peel strength at 120 ° C. is further improved. It becomes high and heat resistance becomes better.
2Lナスフラスコに、40℃に温めたメタノール(900mL)を入れ、ここに、下記式(2)で表されるテレフタルアルデヒド酸(30.0g)を加えて溶かした。この溶液に、下記式(1)で表されるフェニルヒドロキシアミン(21.8g)をメタノール(100mL)に溶かしたものを加え、室温で19時間撹拌した。撹拌終了後、メタノールからの再結晶により、下記式(3)で表されるカルボキシニトロンを得た(41.7g)。収率は86%であった。 <Synthesis of nitrone derivative (carboxy nitrone)>
Methanol (900 mL) warmed to 40 ° C. was placed in a 2 L eggplant flask, and terephthalaldehyde acid (30.0 g) represented by the following formula (2) was added and dissolved therein. To this solution, a solution of phenylhydroxyamine (21.8 g) represented by the following formula (1) dissolved in methanol (100 mL) was added and stirred at room temperature for 19 hours. After completion of stirring, carboxynitrone represented by the following formula (3) was obtained by recrystallization from methanol (41.7 g). The yield was 86%.
2Lナスフラスコに、40℃に温めたメタノール(900mL)を入れ、ここに、下記式(5)で表されるピリジルアルデヒド酸(21.4g)を加えて溶かした。この溶液に、下記式(4)で表されるフェニルヒドロキシアミン(21.8g)をメタノール(100mL)に溶かしたものを加え、室温で19時間撹拌した。撹拌終了後、メタノールからの再結晶により、下記式(6)で表されるピリジルニトロンを得た(39.0g)。収率は90%であった。 <Synthesis of nitrone derivative (pyridyl nitrone)>
Methanol (900 mL) warmed to 40 ° C. was placed in a 2 L eggplant flask, and pyridylaldehyde acid (21.4 g) represented by the following formula (5) was added and dissolved therein. To this solution, a solution of phenylhydroxyamine (21.8 g) represented by the following formula (4) dissolved in methanol (100 mL) was added and stirred at room temperature for 19 hours. After the completion of stirring, pyridyl nitrone represented by the following formula (6) was obtained by recrystallization from methanol (39.0 g). The yield was 90%.
300mLナスフラスコに、下記式(8)で表されるベンズアルデヒド(42.45g)およびエタノール(10mL)を入れ、ここに、下記式(7)で表されるフェニルヒドロキシアミン(43.65g)をエタノール(70mL)に溶かしたものを加え、室温で22時間撹拌した。撹拌終了後、エタノールからの再結晶により、下記式(9)で表されるジフェニルニトロンを白色の結晶として得た(65.40g)。収率は83%であった。 <Synthesis of nitrone derivative (diphenylnitrone)>
Benzaldehyde (42.45 g) represented by the following formula (8) and ethanol (10 mL) are placed in a 300 mL eggplant flask, and phenylhydroxyamine (43.65 g) represented by the following formula (7) is added to ethanol. What was dissolved in (70 mL) was added, and it stirred at room temperature for 22 hours. After completion of stirring, diphenylnitrone represented by the following formula (9) was obtained as white crystals by recrystallization from ethanol (65.40 g). The yield was 83%.
下記第1表に示す成分を、下記第1表に示す割合(質量部)で配合した。
具体的には、まず、容器内の温度を160℃に設定したガラス容器に、スチレン-ブタジエンブロック共重合体および可塑剤を添加し、5分間混練した後、ニトロン誘導体を添加し、更に10分間混練した。
次いで、ガラス容器内の温度を130℃に設定し、充填剤およびタッキファイヤーを添加し、10分間混練した後、老化防止剤を添加し、更に5分間混練した。
その後、混合物を取り出し、冷却することにより、ホットメルト接着剤組成物を調製した。 <Examples 1 to 13>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 below.
Specifically, first, a styrene-butadiene block copolymer and a plasticizer are added to a glass container whose temperature in the container is set to 160 ° C., kneaded for 5 minutes, then a nitrone derivative is added, and further 10 minutes. Kneaded.
Next, the temperature in the glass container was set to 130 ° C., a filler and a tackifier were added, kneaded for 10 minutes, an anti-aging agent was added, and the mixture was further kneaded for 5 minutes.
Thereafter, the mixture was taken out and cooled to prepare a hot melt adhesive composition.
下記第1表に示す成分を、下記第1表に示す割合(質量部)で配合した。
具体的には、スチレン-ブタジエンブロック共重合体等を混練する際のガラス容器内の温度を130℃で行った以外は、実施例1と同様の方法により、ホットメルト接着剤組成物を調製した。 <Example 14>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 below.
Specifically, a hot melt adhesive composition was prepared in the same manner as in Example 1 except that the temperature in the glass container when kneading the styrene-butadiene block copolymer was 130 ° C. .
下記第1表に示す成分を、下記第1表に示す割合(質量部)で配合した。
具体的には、ニトロン誘導体を配合しなかった以外は、実施例1~12と同様の方法により、ホットメルト接着剤組成物を調製した。 <Comparative Examples 1 to 4>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1 below.
Specifically, hot melt adhesive compositions were prepared by the same method as in Examples 1 to 12 except that no nitrone derivative was added.
市販のウレタン系ホットメルト接着剤組成物(ウレタン系HM)を用いた。 <Comparative Examples 5 and 6>
A commercially available urethane hot melt adhesive composition (urethane HM) was used.
各ホットメルト接着剤組成物の120℃、140℃、160℃および180℃における溶融粘度(mPas)を単一円筒回転粘度計を用いて測定した。
また、測定結果から、120℃における溶融粘度と180℃における溶融粘度との比率(120℃粘度/180℃粘度)を算出した。 (Melt viscosity and melt viscosity ratio)
The melt viscosity (mPas) at 120 ° C., 140 ° C., 160 ° C. and 180 ° C. of each hot melt adhesive composition was measured using a single cylindrical rotational viscometer.
Moreover, the ratio (120 degreeC viscosity / 180 degreeC viscosity) of the melt viscosity in 120 degreeC and the melt viscosity in 180 degreeC was computed from the measurement result.
各ホットメルト接着剤組成物の軟化点(℃)をJIS K6863:1994に準拠した、グリセリン浴を用いたリング法にて測定した。 (Softening point)
The softening point (° C.) of each hot melt adhesive composition was measured by a ring method using a glycerin bath based on JIS K6863: 1994.
各ホットメルト接着剤組成物を180℃で溶融させた状態でPET基板(幅:25mm)上に塗布した後、更に同様のサイズのPET基板を貼りあわせ、室温まで徐冷し、試験片を作製した。
作製した試験片における被着体(PET基板)同士を剥離させる180度剥離試験を25℃下で行い、剥離した時の強度(g/25mm)を測定した。
同様の剥離試験を120℃下で行い、剥離した時の強度(g/25mm)を測定した。 (Peel strength)
After each hot melt adhesive composition was melted at 180 ° C. and applied on a PET substrate (width: 25 mm), a PET substrate of the same size was further bonded and slowly cooled to room temperature to produce a test piece. did.
A 180 degree peel test for peeling the adherends (PET substrates) on the prepared test pieces was performed at 25 ° C., and the strength (g / 25 mm) when peeled was measured.
A similar peel test was performed at 120 ° C., and the strength (g / 25 mm) when peeled was measured.
各ホットメルト接着剤組成物を180℃で溶融させた状態で72時間放置した。
72時間放置後の異物(ゲル化状物)の有無を確認した。異物がなければ熱安定性に優れていると評価することができ、異物が存在していれば熱安定性に劣ると評価することができる。 (Thermal stability)
Each hot melt adhesive composition was allowed to stand for 72 hours in a melted state at 180 ° C.
The presence or absence of foreign matter (gelled product) after 72 hours was confirmed. If there is no foreign material, it can be evaluated that the thermal stability is excellent, and if there is a foreign material, it can be evaluated that the thermal stability is poor.
測定結果を対比したところ、実施例1で調製したホットメルト接着剤組成物に由来する重合体には、上記スチレン-ブタジエンブロック共重合体のブタジエン(二重結合)の消失に伴うプロトンのケミカルシフトが確認され、ニトロン誘導体の一部とスチレン-ブタジエンブロック共重合体のブタジエンの二重結合との間に環化付加反応(上記式(I)参照)が生起していることが確認できた。 The hot melt adhesive compositions prepared in Example 1 and Example 14 were washed with cyclohexane to isolate only the polymer, and then 1 H-NMR (proton nuclear magnetic resonance) measurement was performed.
When the measurement results were compared, the polymer derived from the hot melt adhesive composition prepared in Example 1 had a proton chemical shift associated with the disappearance of butadiene (double bond) in the styrene-butadiene block copolymer. It was confirmed that a cycloaddition reaction (see the above formula (I)) occurred between a part of the nitrone derivative and the butadiene double bond of the styrene-butadiene block copolymer.
・SBS1:アサプレンT-439(スチレン/ブタジエン質量比:45/55、旭化成ケミカルズ社製)
・SBS2:アサプレンT-432(スチレン/ブタジエン質量比:30/70、旭化成ケミカルズ社製)
・SBBS:タフテックP1000(スチレン/ブタジエン質量比:30/70、旭化成ケミカルズ社製)
・ニトロン誘導体:上述した方法により合成したカルボキシニトロン、ピリジルニトロン、ジフェニルニトロンを用いた。
・充填剤(シリカ):アエロジル200(日本アエロジル社製)
・タッキファイヤー(テルペン樹脂):クリアロンM105(ヤスハラケミカル社製)
・タッキファイヤー(石油樹脂):ECR5600(トーネックス社製)
・可塑剤(プロセスオイル):ダイアナフレシアS32(出光興産社製)
・老化防止剤(ヒンダードフェノール系):イルガノックス1010(BSAF社製)
・ウレタン系HM1:タイフォース FH-100(DIC社製)
・ウレタン系HM2:ハイボン 4832SA(日立化成社製) Details of each component shown in Table 1 are as follows.
SBS1: Asaprene T-439 (styrene / butadiene mass ratio: 45/55, manufactured by Asahi Kasei Chemicals Corporation)
SBS2: Asaprene T-432 (styrene / butadiene mass ratio: 30/70, manufactured by Asahi Kasei Chemicals)
SBBS: Tuftec P1000 (styrene / butadiene mass ratio: 30/70, manufactured by Asahi Kasei Chemicals Corporation)
Nitron derivative: Carboxynitrone, pyridylnitrone, diphenylnitrone synthesized by the above-described method was used.
・ Filler (silica): Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.)
・ Tackifier (terpene resin): Clearon M105 (manufactured by Yasuhara Chemical)
・ Tack fire (petroleum resin): ECR5600 (manufactured by Tonex)
・ Plasticizer (process oil): Diana Fresia S32 (made by Idemitsu Kosan Co., Ltd.)
Anti-aging agent (hindered phenol type): Irganox 1010 (manufactured by BSAF)
・ Urethane HM1: Tyforce FH-100 (manufactured by DIC)
-Urethane HM2: Hibon 4832SA (manufactured by Hitachi Chemical Co., Ltd.)
また、ニトロン誘導体を配合せずに調製した比較例1~4のホットメルト接着剤組成物は、熱安定性は良好となるが、120℃における剥離強度(耐熱性)に劣ることが分かった。 From the results shown in Table 1 above, it was found that when a commercially available urethane-based hot melt adhesive composition was used, the thermal stability was poor and the peel strength (heat resistance) at 120 ° C. was poor (comparison). Examples 5 and 6).
Further, it was found that the hot melt adhesive compositions of Comparative Examples 1 to 4 prepared without blending the nitrone derivative had good thermal stability but were inferior in peel strength (heat resistance) at 120 ° C.
特に、実施例1と比較例1とを比較すると、ニトロン誘導体の有無により、120℃における溶融粘度が2倍近く上昇し、かつ、180℃における溶融粘度が同等程度となり、ニトロン誘導体を添加することにより、熱安定性および耐熱性だけでなく、塗工時の作業性等も格段に向上したことが分かる。
また、実施例6および7と実施例13との対比から、充填剤としてのシリカの含有量が5質量部以下であると、120℃における剥離強度(耐熱性)が良好となる傾向があることが分かった。
更に、実施例1と実施例14との対比から、混練時の温度が高いと、120℃における剥離強度(耐熱性)が良好となる傾向があることが分かった。これは、上述したように、上記ニトロン誘導体の一部または全部と上記スチレン-ブタジエンブロック共重合体のブタジエンの二重結合との間に環化付加反応(上記式(I)参照)が生起することにより、上記スチレン-ブタジエンブロック共重合体同士の相互作用(分子間力)が高まったためと考えられる。 In contrast, the hot melt adhesive compositions of Examples 1 to 14 prepared by blending a specific amount of a nitrone derivative with a predetermined styrene-butadiene block copolymer are excellent in thermal stability and peel at 120 ° C. It was found that the strength (heat resistance) was also good.
In particular, when Example 1 and Comparative Example 1 are compared, the melt viscosity at 120 ° C. rises almost twice due to the presence or absence of the nitrone derivative, and the melt viscosity at 180 ° C. becomes comparable, and the nitrone derivative is added. Thus, it can be seen that not only the thermal stability and heat resistance, but also the workability at the time of coating has been remarkably improved.
Further, from the comparison between Examples 6 and 7 and Example 13, when the content of silica as a filler is 5 parts by mass or less, the peel strength (heat resistance) at 120 ° C. tends to be good. I understood.
Furthermore, it was found from the comparison between Example 1 and Example 14 that the peel strength (heat resistance) at 120 ° C. tends to be good when the temperature during kneading is high. This is because, as described above, a cycloaddition reaction (see the above formula (I)) occurs between part or all of the nitrone derivative and the butadiene double bond of the styrene-butadiene block copolymer. This is considered to be because the interaction (intermolecular force) between the styrene-butadiene block copolymers was increased.
Claims (6)
- スチレン-ブタジエンブロック共重合体とニトロン誘導体とを含有し、
前記スチレン-ブタジエンブロック共重合体が、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、および/または、スチレン-ブタジエン-ブチレン-スチレンブロック共重合体(SBBS)であり、
前記ニトロン誘導体の含有量が、前記スチレン-ブタジエンブロック共重合体100質量部に対して1~10質量部である、ホットメルト接着剤組成物。 Containing a styrene-butadiene block copolymer and a nitrone derivative,
The styrene-butadiene block copolymer is a styrene-butadiene-styrene block copolymer (SBS) and / or a styrene-butadiene-butylene-styrene block copolymer (SBBS),
A hot melt adhesive composition, wherein the content of the nitrone derivative is 1 to 10 parts by mass with respect to 100 parts by mass of the styrene-butadiene block copolymer. - 120℃における溶融粘度と180℃における溶融粘度との比率(120℃粘度/180℃粘度)が7以上である、請求項1に記載のホットメルト接着剤組成物。 The hot melt adhesive composition according to claim 1, wherein the ratio of the melt viscosity at 120 ° C to the melt viscosity at 180 ° C (120 ° C viscosity / 180 ° C viscosity) is 7 or more.
- 180℃における溶融粘度が4000mPas以下である、請求項2に記載のホットメルト接着剤組成物。 The hot melt adhesive composition according to claim 2, wherein the melt viscosity at 180 ° C is 4000 mPas or less.
- 前記ニトロン誘導体が、置換基を有していてもよい芳香族炭化水素基または芳香族複素環基を有するニトロンである、請求項1~3のいずれかに記載のホットメルト接着剤組成物。 The hot melt adhesive composition according to any one of claims 1 to 3, wherein the nitrone derivative is a nitrone having an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
- 前記ニトロン誘導体が、前記置換基としてカルボキシ基を有する請求項4に記載のホットメルト接着剤組成物。 The hot melt adhesive composition according to claim 4, wherein the nitrone derivative has a carboxy group as the substituent.
- シリカの含有量が、前記スチレン-ブタジエンブロック共重合体100質量部に対して5質量部以下である、請求項1~5のいずれかに記載のホットメルト接着剤組成物。 6. The hot melt adhesive composition according to claim 1, wherein the silica content is 5 parts by mass or less based on 100 parts by mass of the styrene-butadiene block copolymer.
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KR1020157025286A KR101622324B1 (en) | 2013-03-08 | 2014-03-07 | Hot-melt-adhesive composition |
CN201480025871.7A CN105209566B (en) | 2013-03-08 | 2014-03-07 | Hot-melt adhesive composition |
PH12015501989A PH12015501989A1 (en) | 2013-03-08 | 2015-09-07 | Hot melt adhesive composition |
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JP2013046627A JP5578249B1 (en) | 2013-03-08 | 2013-03-08 | Hot melt adhesive composition |
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PCT/JP2014/055975 WO2014136940A1 (en) | 2013-03-08 | 2014-03-07 | Hot-melt-adhesive composition |
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JP (1) | JP5578249B1 (en) |
KR (1) | KR101622324B1 (en) |
CN (1) | CN105209566B (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107250244A (en) * | 2015-03-19 | 2017-10-13 | 横滨橡胶株式会社 | Rubber composition for tire tread and pneumatic tire |
WO2018151190A1 (en) * | 2017-02-17 | 2018-08-23 | 積水フーラー株式会社 | Hot melt adhesive and stretchable laminate |
CN112772005A (en) * | 2018-09-25 | 2021-05-07 | 积水富乐株式会社 | Hot melt coating agent for electronic circuit mounting substrate |
US11312886B2 (en) | 2016-04-08 | 2022-04-26 | Avery Dennison Corporation | Clear hot melt adhesives |
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WO2018070676A1 (en) * | 2016-10-14 | 2018-04-19 | 박희대 | Reactive hot melt resin composition and reactive hot melt film manufactured from resin |
JP7060885B2 (en) * | 2019-12-11 | 2022-04-27 | 誠泰工業科技股▲分▼有限公司 | Eco-waterproof hot melt adhesive composition, its film material and manufacturing method |
KR102309698B1 (en) | 2020-01-16 | 2021-10-07 | 주식회사 이레A.T (에이티) | Hot melt adhesive with excellent durability and adhesion |
JPWO2022181690A1 (en) * | 2021-02-26 | 2022-09-01 |
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- 2014-03-07 CN CN201480025871.7A patent/CN105209566B/en not_active Expired - Fee Related
- 2014-03-07 WO PCT/JP2014/055975 patent/WO2014136940A1/en active Application Filing
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JPS60500957A (en) * | 1983-03-30 | 1985-06-27 | スコツト、ジエラルド | stabilized rubber composition |
JP2011506650A (en) * | 2007-12-12 | 2011-03-03 | ハインリヒ−ハイネ−ウニベルジテート | Polynitrones and their use to crosslink unsaturated polymers |
JP2013032471A (en) * | 2011-08-03 | 2013-02-14 | Yokohama Rubber Co Ltd:The | Rubber composition |
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CN107250244A (en) * | 2015-03-19 | 2017-10-13 | 横滨橡胶株式会社 | Rubber composition for tire tread and pneumatic tire |
US11312886B2 (en) | 2016-04-08 | 2022-04-26 | Avery Dennison Corporation | Clear hot melt adhesives |
WO2018151190A1 (en) * | 2017-02-17 | 2018-08-23 | 積水フーラー株式会社 | Hot melt adhesive and stretchable laminate |
JPWO2018151190A1 (en) * | 2017-02-17 | 2019-02-21 | 積水フーラー株式会社 | Hot melt adhesive and stretch laminate |
CN112772005A (en) * | 2018-09-25 | 2021-05-07 | 积水富乐株式会社 | Hot melt coating agent for electronic circuit mounting substrate |
EP3860318A4 (en) * | 2018-09-25 | 2022-06-15 | Sekisui Fuller Company, Ltd. | Hot melt coating agent for component-mounted electronic circuit board |
Also Published As
Publication number | Publication date |
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KR20150142674A (en) | 2015-12-22 |
JP2014172995A (en) | 2014-09-22 |
CN105209566B (en) | 2017-12-05 |
JP5578249B1 (en) | 2014-08-27 |
PH12015501989B1 (en) | 2016-01-11 |
PH12015501989A1 (en) | 2016-01-11 |
CN105209566A (en) | 2015-12-30 |
KR101622324B1 (en) | 2016-05-18 |
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