Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • 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
• • 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
  • C09J123/10—Homopolymers or copolymers of propene
  • C09J123/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
  • C09J125/02—Homopolymers or copolymers of hydrocarbons
  • C09J125/04—Homopolymers or copolymers of styrene
  • C09J125/08—Copolymers of styrene
• • 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
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

• the present invention relates to hot melt adhesives.
• Double-sided tape has a long open time and exhibits adhesive strength immediately after bonding at room temperature, but it is necessary to tear off the tape after bonding to the adherend and peel off the release paper used on the adhesive surface Therefore, there is a problem that automation by a robot is difficult and productivity decreases.
• Hot melt adhesives have been used as an alternative to double-sided tape.
• Hot-melt adhesives are non-solvent adhesives, and are used in the fields of automobiles, electrics and electronics, and the like, because they are capable of bonding in a short period of time.
• hot-melt adhesives of Patent Documents 1 to 4 have been proposed.
• Patent Document 1 describes a hot melt adhesive containing an isotactic polypropylene random copolymer.
• Patent Document 2 describes a hot-melt adhesive containing a glassy poly- ⁇ -olefin copolymer.
• Patent Document 3 describes a hot melt adhesive containing a styrene-isobutylene-styrene triblock copolymer.
• Patent Document 4 describes a hot melt adhesive containing a styrenic block copolymer.
• the hot melt adhesive described in Patent Document 1 has a problem of poor heat resistance due to its low softening point, and a problem of being difficult to apply to spiral sprays due to its high melt viscosity. .
• An object of the present invention is to provide a hot melt adhesive that can be applied at a low temperature, has excellent heat resistance and adhesiveness, and has a moderately long open time and a short set time.
• the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have succeeded in developing a hot melt adhesive having specific physical property values. found that it is possible to achieve The present invention was completed by the present inventors through further research.
• Section 1 A hot melt adhesive having a ring and ball softening point of 140°C or higher and a melt viscosity of 3000 mPa s or lower at 163°C, Dynamic viscoelasticity measurement (heating method) was performed under the conditions of a rotational shear mode with a vibration frequency of 1 Hz, a heating rate of 5 ° C./min, and a temperature range of -40 ° C. to 200 ° C., and measured by the heating method.
• T1 The highest temperature at which tan ⁇ (loss modulus G′′/storage modulus G′) becomes 1 is T1
• Dynamic viscoelasticity measurement temperature drop method
• T2 Dynamic viscoelasticity measurement (temperature drop method) was performed under the conditions of a rotational shear mode with a vibration frequency of 1 Hz, a temperature drop rate of 5 ° C./min, and a temperature range of 200 ° C. to -40 ° C.
• T2 A hot melt adhesive in which the difference between T1 and T2 is 20 °C or more.
• the hot melt adhesive according to Item 1 wherein the temperature at which the storage elastic modulus G' measured by the temperature rising method is 1000 Pa or more is 133°C or more.
• Item 3. a homopropylene polymer (A); a styrenic block copolymer (B1) and/or an olefinic block copolymer (B2); a tackifier resin (C); 3.
• Item 3 The hot melt adhesive according to Item 3, further comprising a polyolefin wax (D).
• the hot melt adhesive according to item 4 wherein the polyolefin wax (D) is an unmodified polypropylene wax (D1).
• Item 6. Item 6.
• the hot melt adhesive according to Item 5 wherein the unmodified polypropylene wax (D1) has a melt viscosity at 170° C. of 4500 to 7000 mPa ⁇ s.
• Item 7. Item 7. The hot melt adhesive according to any one of Items 3 to 6, wherein the homopropylene polymer (A) has a melt viscosity of 1200 to 14000 mPa ⁇ s at 170°C.
• the styrenic block copolymer (B1) has a melt flow rate of 200 to 400 g/10 minutes (230°C, 2.16 kg).
• the styrene block copolymer (B1) is a styrene-ethylene-butylene-styrene block copolymer (SEBS), 10.
• SEBS styrene-ethylene-butylene-styrene block copolymer
• the hot melt adhesive according to Item 9 wherein the polyolefin wax (D) is an unmodified polypropylene wax (D1).
• Item 11. 11 The hot melt adhesive according to Item 10, wherein the unmodified polypropylene wax (D1) has a melt viscosity at 170° C.
• the hot melt adhesive of the present invention can be applied at a low temperature, has excellent heat resistance and adhesiveness, and has a moderately long open time and short set time.
• the upper limit or lower limit of the numerical range at one stage can be arbitrarily combined with the upper limit or lower limit of the numerical range at another stage.
• the upper or lower limit of the numerical range may be replaced with values shown in Examples or values that can be uniquely derived from Examples.
• a numerical value connected with "-" means a numerical range including the numerical values before and after "-" as lower and upper limits.
• a and/or B means either one of A and B, or both A and B.
• low temperature means 150 to 165°C.
• hot melt adhesives are often used at 180° C. or higher.
• melt viscosity means the viscosity (mPa ⁇ s) of a hot-melt adhesive that has been heated and melted at a certain temperature.
• the hot melt adhesive of the present invention is (1) a ring and ball softening point of 140° C. or higher; (2) a melt viscosity of 3000 mPa s or less at 163°C; (3) Perform dynamic viscoelasticity measurement (heating method) by heating from -40 ° C. to 200 ° C. at a rotational shear mode with a vibration frequency of 1 Hz and a heating rate of 5 ° C./min.
• the temperature is lowered from 200 ° C. to ⁇ 40. ° C. and perform dynamic viscoelasticity measurement (temperature cooling method), the highest temperature T2 at which tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) measured by the cooling method becomes 1 , and The difference (T 1 -T 2 ) is 20° C. or more.
• the hot-melt adhesive of the present invention (1) has a ring and ball softening point of 140°C or higher, so it has excellent heat resistance, and has a moderately long open time and short set time.
• a moderately long open time means preferably 10 seconds or more and 100 seconds or less
• a short set time means preferably 1 second or more and 5 seconds or less.
• the hot melt adhesive of the present invention (2) has a melt viscosity of 3000 mPa ⁇ s or less at 163°C, so that it can be applied at low temperatures.
• the hot-melt adhesive of the present invention has a moderately long open time because (3) T 1 -T 2 is 20° C. or more.
• the hot-melt adhesive of the present invention has the above-mentioned (1), (2) and (3), so that it can be applied at a low temperature, has excellent heat resistance and adhesiveness, and has an appropriate length. It has a short open time and a short set time.
• the hot melt adhesive of the present invention may be simply referred to as "the present invention”.
• the ring and ball softening point is preferably 140 to 160°C, more preferably 142 to 158°C, and even more preferably 145 to 155°C, from the viewpoint of better heat resistance.
• the melt viscosity at 163° C. is preferably 500 to 3,000 mPa s, more preferably 700 to 2,800 mPa s, from the viewpoints of being excellent in low-temperature coating, protecting the substrate, and facilitating handling. More preferably 800 to 2600 mPa ⁇ s, particularly preferably 1000 to 2500 mPa ⁇ s.
• the dynamic viscoelasticity measurement is measured in rotational shear mode with the vibration frequency fixed at 1 Hz. Specifically, the dynamic viscoelasticity measurement is performed in the following manner.
• release paper Prepare two pieces of release paper (hereinafter referred to as "release paper") that has undergone a release treatment.
• a melted hot-melt adhesive is dripped onto the release-treated surface of one of the release papers.
• another release paper that has been subjected to a release treatment is superposed on the dropped hot-melt adhesive so that the release-treated surface of the release paper comes into contact with the hot-melt adhesive.
• it is compressed with a hot press heated to 100° C., and adjusted so that the thickness of the hot-melt adhesive between release papers is about 2 mm.
• the release papers are removed to prepare a sample for dynamic viscoelasticity measurement.
• the prepared sample is mounted on a dynamic viscoelasticity measuring device, and in a rotational shear mode with a vibration frequency of 1 Hz, the temperature is raised from -40 ° C. to 200 ° C. at a heating rate of 5 ° C./min to measure dynamic viscoelasticity ( After that, the temperature is lowered from 200° C. to ⁇ 40° C. at a rate of 5° C./min, and dynamic viscoelasticity measurement (temperature drop method) is performed.
• the dynamic viscoelasticity measuring device include a rotational rheometer (product name: "AR-G2") available from TA Instruments.
• T 1 is the highest temperature (° C.) at which tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) measured by the temperature rising method at a vibration frequency of 1 Hz by dynamic viscoelasticity measurement becomes 1.
• T 2 is the highest temperature (° C.) at which tan ⁇ (loss modulus G′′/storage modulus G′) is 1 measured by the cooling method at a frequency of 1 Hz by dynamic viscoelasticity measurement
• T 1 and T 2 (T 1 -T 2 ) is 20° C. or more.
• T 1 -T 2 is preferably 30° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, and particularly preferably 55° C. or higher.
• T 1 is the highest temperature (° C.) at which tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) measured by the temperature rising method at a vibration frequency of 1 Hz by dynamic viscoelasticity measurement becomes 1.
• T 2 is the highest temperature (° C.) at which tan ⁇ (loss modulus G′′/storage modulus G′) is 1 measured by the cooling method at a frequency of 1 Hz by dynamic viscoelasticity measurement
• T 1 and T 2 is preferably 90°C or less, more preferably 80°C or less, even more preferably 75°C or less, and particularly preferably 70°C or less.
• Dynamic viscoelasticity measurement is a method for analyzing the mechanical properties of polymers that have both elasticity and viscosity.
• the dynamic viscoelasticity measurement it is possible to measure the storage elastic modulus G′ and the loss elastic modulus G′′, the storage elastic modulus G′ being a characteristic value corresponding to elasticity, and the loss elastic modulus G′′ is the corresponding characteristic value.
• the temperature at which tan ⁇ (loss modulus G′′/storage modulus G′) measured by the heating method in a rotational shear mode with a vibration frequency of 1 Hz becomes 1 is called the crossover point.
• the crossover point is a measure of the temperature at which it changes from solid to liquid or from liquid to solid.
• the highest temperature (° C.) T at which tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) measured in a rotational shear mode with a vibration frequency of 1 Hz by dynamic viscoelasticity measurement is 1
• T 1 the temperature (°C) measured by the above temperature rising method
• T 2 the temperature (°C) measured by the above temperature decreasing method
• dynamic viscoelasticity measurement (heating method) is performed under the conditions of a rotational shear mode with a vibration frequency of 1 Hz, a temperature increase rate of 5 ° C./min, and a temperature range of -40 ° C. to 200 ° C., and the temperature increase method.
• the temperature at which the storage elastic modulus G′ measured by the method becomes 1000 Pa or higher is preferably 133° C. or higher, more preferably 133.5° C. or higher, and still more preferably 134° C. or higher, from the viewpoint of superior heat resistance.
• the temperature at which the storage elastic modulus G′ measured by the temperature rising method is 1000 Pa or more is preferably 160° C. or less, more preferably 155° C. or less, and still more preferably 150° C. or less from the viewpoint of coatability.
• the hot-melt adhesive of the present invention may be simply referred to as "the present invention”.
• Homopropylene polymer (A) In the present invention, it is preferable to use a homopropylene polymer as component (A).
• a homopropylene polymer is a homopolymer of propylene.
• the homopropylene polymer (A) preferably has a ring and ball softening point of 83 to 165°C in view of its excellent heat resistance.
• the ring and ball softening point of the homopropylene polymer (A) is a temperature measured according to JIS K 6863.
• the homopropylene polymer (A) has a melt viscosity at 170° C. of preferably 1,200 to 14,000 mPa ⁇ s, more preferably 1,500 to 8,000 mPa ⁇ s, from the viewpoint of facilitating low-temperature coating. It is preferably 2000 to 5000 mPa ⁇ s.
• the content of the homopropylene polymer (A) in 100% by mass of the hot melt adhesive of the present invention is preferably 10 to 40% by mass, more preferably 12 to 37% by mass, and still more preferably, from the viewpoint of cohesive force. is 15 to 35% by weight, particularly preferably 20 to 30% by weight.
• homopropylene polymer (A) As the homopropylene polymer (A), a wide range of known commercial products can be used. Commercially available products include, for example, the product name "Eastoflex P1023” manufactured by Eastman Chemical Company, and the product name “Rextac RT-2180” manufactured by Rexen.
• styrene-based block copolymer as the (B1) component and/or an olefin-based block copolymer as the (B2) component.
• styrenic block copolymer (B1) it is more preferable to use only the styrenic block copolymer (B1) as the block copolymer.
• the styrenic block copolymer (B1) may be either unhydrogenated or hydrogenated.
• examples of the styrene block copolymer (B1) include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer.
• styrene-butadiene-butylene-styrene block copolymer SBBS
• styrene-ethylene-propylene-styrene block copolymer SEPS
• styrene-ethylene-butylene-olefin crystal block copolymer SEBC
• SEBS styrene-ethylene-butylene-olefin crystal block copolymer
• the styrene skeleton content in the styrene block copolymer (B1) is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and 20 to 45% by mass in 100% by mass of the styrene block copolymer (B1). % by mass is even more preferred.
• the styrene skeleton content ratio refers to the content ratio (mass%) of the styrene block in the styrene-based block copolymer (B1).
• Examples of the method for calculating the content of the styrene skeleton in the styrene block copolymer (B1) include methods using proton nuclear magnetic resonance, infrared spectroscopy, etc. according to JIS K6239.
• styrene-based block copolymer (B1) As the styrene-based block copolymer (B1), a wide range of known commercial products can be used. Commercially available products include, for example, the product name "MD1648” manufactured by Clayton Polymer Co., Ltd., the product name "G1726” manufactured by Clayton Polymer Co., Ltd., the product name "SEPTON2002” manufactured by Kuraray Co., Ltd., and the product name "DYNARON4600P” manufactured by JSR Corporation. mentioned.
• the content of the styrenic block copolymer (B1) in 100% by mass of the hot melt adhesive of the present invention is preferably 3 to 30% by mass, more preferably 4%, from the viewpoint of adjusting the melt viscosity to an appropriate range. ⁇ 25 wt%, more preferably 5 to 20 wt%.
• the melt flow rate (MFR) of the styrenic block copolymer (B1) is preferably 200 to 400 g/10 minutes (230°C, 2.16 kg), more preferably 200 to 300 g/10 minutes (230°C, 2.16 kg). 16 kg), more preferably 200-250 g/10 min (230° C., 2.16 kg).
• the melt flow rate (MFR) of the styrenic block copolymer (B1) is the MFR (g/10 minutes) measured under conditions of a temperature of 230°C and a load of 2.16 kg based on ASTM D1238.
• Olefin block copolymer (B2) As the olefinic block copolymer (B2), an olefinic crystal block copolymer is preferred.
• CEBC olefin crystal-ethylene/butylene-olefin crystal block copolymer
• olefin block copolymer (B2) As the olefin block copolymer (B2), a wide range of known commercial products can be used. Commercially available products include, for example, CEBC, product name "DYNARON6200P” manufactured by JSR Corporation.
• the content of the olefin block copolymer (B2) in 100% by mass of the hot melt adhesive of the present invention is preferably 1 to 20% by mass, more preferably 2% by mass, from the viewpoint of adjusting the melt viscosity to an appropriate range. ⁇ 15 wt%, more preferably 3 to 10 wt%.
• Tackifying resin (C) In the present invention, it is preferable to use a tackifying resin as the component (C).
• the tackifying resin (C) include rosin-based compounds, terpene-based compounds, and petroleum resins. These tackifying resins (C) can be used alone or in combination of two or more. Among these tackifying resins (C), terpene compounds and petroleum resins are preferred, and petroleum resins (especially hydrogenated petroleum resins) are particularly preferred.
• rosin compounds include natural rosin, modified rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, and pentaerythritol ester of modified rosin.
• Terpene compounds include, for example, natural terpene copolymers, natural terpene three-dimensional polymers, hydrogenated derivatives of natural terpene copolymers, terpene resins, and hydrogenated derivatives of phenolic modified terpene resins.
• Examples of petroleum resins include petroleum resins such as C5 petroleum resins, C9 petroleum resins, C5C9 petroleum resins, dicyclopentadiene petroleum resins, and partially hydrogenated petroleum resins obtained by adding hydrogen to these petroleum resins.
• Examples include hydrogenated petroleum resins.
• the C5 petroleum resin is a petroleum resin made from a C5 fraction of petroleum
• the C9 petroleum resin is a petroleum resin made from a C9 fraction of petroleum
• the C5C9 petroleum resin is a petroleum resin. It is a petroleum resin made from a C5 fraction and a C9 fraction.
• C5 fractions include cyclopentadiene, isoprene, pentane, and the like.
• the C9 fraction includes styrene, vinyltoluene, indene, and the like.
• the C9-based petroleum resin and the C5C9-based petroleum resin those containing styrene, which is a type of C9 fraction, in the skeleton are preferred.
• tackifier resin (C) petroleum resins are preferable, and partially hydrogenated petroleum resins and fully hydrogenated petroleum resins are more preferable, in terms of excellent thermal stability of the hot-melt adhesive.
• the tackifying resin (C) described above can be used alone or in combination of two or more.
• the ring and ball softening point of the tackifying resin (C) is preferably 90°C or higher, more preferably 100°C or higher.
• the upper limit of the ring and ball softening point is preferably 140°C.
• the hot melt adhesive of the present invention tends to exhibit good adhesiveness.
• the ring and ball softening point of the tackifying resin (C) is a temperature measured according to JIS K 6863.
• the content of the tackifying resin (C) in 100% by mass of the hot melt adhesive of the present invention is preferably 40% by mass or more. In this case, the adhesiveness of the hot-melt adhesive is improved and the adhesion to the adherend is improved. Moreover, the content of the tackifying resin (C) in 100% by mass of the hot melt adhesive of the present invention is preferably 60% by mass or less. In this case, the hot-melt adhesive becomes soft and easily exhibits adhesive strength.
• tackifying resin (C) As the tackifying resin (C), a wide range of known commercial products can be used. Commercially available products include, for example, the product name "Easttac C100L” manufactured by Eastman Chemical Co., Ltd., the product name “imarv P-100” manufactured by Idemitsu Kosan Co., Ltd., and the product name "Alcon P-100” manufactured by Arakawa Chemical Industries. ” and the like.
• Polyolefin wax (D) In the present invention, it is preferable to use polyolefin wax as the component (D).
• Polyolefin wax (D) is a polymer of olefin monomers such as ethylene, propylene, 1-butene, isobutylene and 1-pentene.
• the polyolefin wax obtained from these monomers may be a homopolymer type obtained from one type of monomer, or a copolymer type obtained from two or more types of monomers. good.
• the polyolefin wax (D) is preferably polypropylene wax.
• the polyolefin wax (D) is preferably unmodified polypropylene wax (D1). That is, the hot melt adhesive of the present invention preferably contains unmodified polypropylene wax (D1).
• Unmodified polypropylene wax (D1) means polypropylene wax that has not been acid-modified with an unsaturated carboxylic acid or its acid anhydride.
• unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, acrylic anhydride, and methacrylic anhydride.
• the ring and ball softening point of the unmodified polypropylene wax (D1) is preferably 55 to 170° C., more preferably 65 to 165° C., still more preferably 65 to 165° C., from the viewpoint of achieving both a moderately long open time and a short set time. is 70 to 160°C, particularly preferably 75 to 155°C.
• the ring and ball softening point of unmodified polypropylene wax (D1) is a temperature measured according to JIS K 6863.
• the unmodified polypropylene wax (D1) preferably has a melt viscosity of 4,500 to 7,000 mPa ⁇ s, more preferably 5,000 to 7,000 mPa ⁇ s at 170°C from the viewpoint of facilitating low-temperature coating.
• the content of the unmodified polypropylene wax (D1) in 100% by mass of the hot melt adhesive of the present invention is preferable from the viewpoint of achieving both a moderately long open time and a short set time and excellent heat resistance. is 2 to 20% by mass, more preferably 3 to 18% by mass, even more preferably 5 to 15% by mass, and particularly preferably 6 to 12% by mass.
• a wide range of known commercial products can be used as the unmodified polypropylene wax (D1).
• Examples of commercially available products include Clariant's product name “Ricosene PP1602”, Clariant's product name “Ricosene PP6102”, and Mitsui Chemicals' product name "Hi-Wax NP105”.
• Antioxidant (E) In the present invention, it is preferable to use an antioxidant as the component (E).
• antioxidant a wide range of known antioxidants can be used, such as 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5' -di-t-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,4- Bis(octylthiomethyl)-o-cresol, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-t -amyl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl) ] Hindered phenol antioxidant
• antioxidant a wide range of known commercial products can be used.
• Commercially available products include the product name "IRGANOX1010" manufactured by BASF.
• the content of the antioxidant in 100% by mass of the hot melt adhesive of the present invention is preferably 0.01 to 2% by mass, more preferably 0.05 to 1.5% by mass, and still more preferably 0.1%. to 1% by weight, particularly preferably 0.3 to 0.8% by weight.
• the hot melt adhesive has improved thermal stability and reduced odor.
• the hot-melt adhesive of the present invention may contain various additives, as required, to the extent that the objects of the present invention are not essentially hindered.
• various additives include plasticizers, ultraviolet absorbers, liquid rubbers, fine particle fillers, and the like.
• plasticizer a wide range of known plasticizers can be used, including paraffinic process oil, naphthenic process oil, aromatic process oil, liquid paraffin oil, and hydrocarbon synthetic oil.
• UV absorber a wide range of known UV absorbers can be used, such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-t -Butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole and other benzotriazole-based UV absorbers; 2-hydroxy-4-methoxy benzophenone-based ultraviolet absorbers such as benzophenone; salicylic acid ester-based ultraviolet absorbers; cyanoacrylate-based ultraviolet absorbers; and hindered amine-based light stabilizers. These ultraviolet absorbers may be used alone or in combination of two or more.
• liquid rubber a wide range of known liquid rubbers can be used, including liquid polybutene, liquid polybutadiene, liquid polyisoprene, and hydrogenated resins thereof. These liquid rubbers can be used alone or in combination of two or more.
• fine particle filler a wide range of known fine particle fillers can be used, and examples include calcium carbonate, kaolin, talc, titanium oxide, mica, and styrene beads. These particulate fillers can be used alone or in combination of two or more.
• the content of the various additives (excluding the plasticizer) in 100% by mass of the hot melt adhesive of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less.
• the content of the plasticizer in 100% by mass of the hot melt adhesive of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less. It is particularly preferred that the hot melt adhesive of the present invention does not contain a plasticizer.
• the hot melt adhesive of the present invention comprises a homopropylene polymer (A); a styrene block copolymer (B1) or an olefin block copolymer (B2); a tackifying resin (C); an unmodified polypropylene wax (D1 ); and antioxidant (E).
• the hot-melt adhesive of the present invention comprises only a homopropylene polymer (A); a styrenic block copolymer (B1); a tackifying resin (C); an unmodified polypropylene wax (D1); and an antioxidant (E). Most preferably, it consists of
• the method for producing a hot melt adhesive is not particularly limited, and examples include homopropylene polymer (A), styrene block copolymer (B1) and/or olefin block copolymer. (B2), a tackifying resin (C), a polyolefin wax (D) and an antioxidant (E), and various additives added as necessary are put into a stirring kneader equipped with a heating device and heated. For example, a method of kneading while
• the heating temperature during kneading is not particularly limited, preferably 100 to 200°C, more preferably 120 to 180°C.
• the kneading time is not particularly limited, preferably 40 to 140 minutes, more preferably 60 to 120 minutes.
• Coating method and use of hot-melt adhesive As a coating method for coating the hot-melt adhesive of the present invention, known coating methods can be widely used, for example, spiral spray coating, slot coater coating, curtain spray. Coating, roll coater coating, omega coating, dot coating, bead coating and the like can be mentioned. Among these coating methods, spiral spray coating is preferable because non-contact coating is possible, planar coating is possible on a three-dimensional substrate, and rapid coating is possible. .
• Non-contact coating refers to a coating method in which the ejector does not come into contact with the member, film, or the like when coating the hot melt adhesive.
• the hot-melt adhesive of the present invention is particularly suitable for spiral spray coating.
• a coating device for coating the hot-melt adhesive of the present invention on the adhesive part a wide range of known coating devices can be used, for example, a hot-melt applicator.
• a hot-melt applicator for example, the product name "REKA handgun TR80LCD (spray)" manufactured by Suntool Co., Ltd. may be used.
• the hot-melt adhesive of the present invention is heated and melted, applied to the adherend portion of the adherend, brought into contact with another adherend in the molten state in which it has been applied, and then cooled and solidified. Join the adherends.
• the material forming the adherend is not particularly limited, and examples thereof include synthetic resins such as polyethylene, polyester, polyvinyl chloride, polyurethane, polypropylene, ABS resin, polymethacrylate, and polycarbonate; cellulosic materials such as paper, board, and cardboard. etc.
• the hot-melt adhesive of the present invention is suitably used for applications such as assembly of tapes, automobile interior parts, home appliance parts, and the like.
• the hot-melt adhesive of the present invention is particularly suitable for automobile interior parts.
• the thickness of the adhesive layer is preferably 1 to 200 ⁇ m, more preferably 1 to 100 ⁇ m.
• the thickness is not limited to these, and can be appropriately set within a range of preferably 1 to 200 ⁇ m depending on the application such as assembly of tapes, automotive interior parts, home appliance parts, and the like.
• melt flow rate (MFR) of "MD1648" used as the styrenic block copolymer (B1-1) is the MFR ( g/10 min).
• melt viscosity evaluation test (163 ° C. melt viscosity evaluation test)
• the hot melt adhesive is heated and melted, and in accordance with the Japan Adhesive Industry Association Standard JAI-7, using a Brookfield RVF type viscometer and thermocel, spindle 4-27, rotation speed 20 rpm, hot at 163 ° C.
• the melt viscosity (mPa ⁇ s) of each melt adhesive was measured. The measurement results are shown in Table 1, "Melt viscosity at 163°C (mPa ⁇ s)".
• the hot-melt adhesive was heated and melted at 160° C. and dropped onto the release layer side of the release-treated polyethylene terephthalate (PET) film.
• PET polyethylene terephthalate
• another release-treated PET film was laminated on the hot-melt adhesive so that the surface on the release layer side was in contact with the hot-melt adhesive.
• it was compressed with a hot press heated to 100° C. to adjust the thickness of the hot-melt adhesive to about 2 mm.
• the release film was removed to prepare a sample for dynamic viscoelasticity measurement.
• the prepared sample was mounted on a dynamic viscoelasticity measuring device (rotational rheometer manufactured by TA Instruments, product name “AR-G2”), and was measured in a rotational shear mode with a vibration frequency of 1 Hz, from -40 ° C. to 200.
• the temperature was raised to 5°C/min to measure dynamic viscoelasticity (heating method).
• the loss elastic modulus G′′ (Pa) and storage elastic modulus G′ (Pa) are measured by the temperature rising method, and the highest temperature at which the loss tangent tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) becomes 1. (° C ) was taken as T1.
• dynamic viscoelasticity measurement (cooling method) was performed by decreasing the temperature from 200° C.
• the loss elastic modulus G′′ (Pa) and storage elastic modulus G′ (Pa) are measured by the cooling method, and the highest temperature at which the loss tangent tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) becomes 1 ( ° C ) was taken as T2.
• T 1 (° C.), T 2 (° C.) and T 1 ⁇ T 2 (° C.) are shown in Table 1 “Dynamic Viscoelasticity Evaluation Test”.
• the temperature (° C.) at which the storage elastic modulus G′ measured by the temperature elevation method was 1000 Pa or more was also measured. The results are shown in Table 1, "Dynamic Viscoelasticity Evaluation Test.”
• a hot-melt adhesive was supplied to a heating and melting tank, and heated to 160° C. to be in a molten state.
• Two transparent PET films were prepared.
• a hot melt adhesive was applied onto the first PET film by spiral spray coating using a hot melt coating machine under the coating conditions of a coating width of 10 mm and a coating amount of 0.05 g/cm. The line speed during coating was set to 1.2 m/min.
• a second PET film was laminated on the hot-melt adhesive-coated surface of the first PET film to prepare a laminated film.
• a test piece was obtained by pressing the laminate film in its thickness direction at 23° C. and a pressure of 0.05 Mpa for 2 seconds.
• the pattern of the hot-melt adhesive was visually observed through the PET film, and the coatability of the hot-melt adhesive was evaluated according to the following evaluation criteria.
• the evaluation results are shown in Table 1, "Coatability Evaluation Test”. If there is an evaluation of ⁇ or higher, it is evaluated that there is no problem in actual use. ⁇ Evaluation Criteria> ⁇ : The pattern of spiral spray coating was clearly confirmed. ⁇ : In the spiral spray coating pattern, the coating width varies by 10 ⁇ 3 mm, but there was no problem in use. x: The pattern of spiral spray coating was disturbed.
• the open time is the time from applying a hot melt adhesive to one side of one adherend to laminating the other adherend on the hot melt adhesive coated side of one adherend. indicate the time. Further, the material destruction rate was defined as the ratio (percentage) of the area of the portion where the adherend was destroyed to the area of the entire bonding surface between the adherends.
• Laminate the other adherend on the surface apply a press load of 0.5 kg for a predetermined time (1 second, 2 seconds, 3 seconds, . . . 1 minute) as a set time, and adhere.
• a press load of 0.5 kg for a predetermined time (1 second, 2 seconds, 3 seconds, . . . 1 minute) as a set time, and adhere.
• one adherend is subjected to a 180 ° peel test at a peel speed of 100 mm / min from one end to the other end in the length direction, and the shortest material destruction rate is 80% or more. I measured the set time. The measurement results are shown in Table 1, "Set time evaluation test.”
• Set time refers to the time during which a press load is applied to the bonded adherends. Further, the material destruction rate was defined as the ratio (percentage) of the area of the portion where the adherend was destroyed to the area of the entire bonding surface between the adherends.
• Hot resistant creep resistance evaluation test 1 A hot-melt adhesive is applied to an acrylic plate with a thickness of 2 mm using a coating device (product name “REKA handgun TR80LCD (spray)” manufactured by Suntool Co., Ltd.), a 2 mm-thick acrylic plate is stacked, and a pressure roller with a mass of 2 kg is applied.
• a test piece was prepared by reciprocating and pasting (adhesion part area 25 mm ⁇ 25 mm). The test piece was heated at a predetermined temperature and time (60 ° C. ⁇ 30 minutes ⁇ 80 ° C. ⁇ 30 minutes ⁇ 100 ° C. ⁇ 30 minutes), a load of 100 g was applied to the edge of the test piece in the shear direction, and the time until the test piece dropped (holding time) was measured and evaluated according to the following evaluation criteria.
• "X” in the evaluation criteria below means that the holding time was less than 30 minutes when a load of 100 g was applied to the edge of the test piece in the shear direction at 60°C for 30 minutes.
• " ⁇ ” in the following evaluation criteria means that when a load of 100 g is applied to the end of the test piece in the shear direction at 60 ° C. for 30 minutes, and then a load of 100 g is applied at 80 ° C. for 30 minutes, the retention time is It means that it was 30 minutes or more and less than 60 minutes.
• " ⁇ ” in the following evaluation criteria means that a load of 100 g is applied to the end of the test piece at 60 ° C. in the shear direction for 30 minutes, followed by a load of 100 g at 80 ° C.
• Hot resistant creep resistance evaluation test 2 A hot-melt adhesive is applied to a styrofoam plate with a thickness of 8 mm using a coating device (product name "REKA hand gun TR80LCD (spray)” manufactured by Suntool Co., Ltd.), and a soft vinyl chloride coated cord (for 200 V) with a diameter of 13 mm is overlaid.
• a test piece was prepared by reciprocating with a pressure roller with a mass of 2 kg and pasting it together (bonded part length 80 mm). °C x 30 minutes), the soft vinyl chloride-coated cord was hung downward, and the time until the test piece dropped (holding time) was measured and evaluated according to the following evaluation criteria.
• a in the evaluation criteria below means that the holding time was less than 30 minutes when a load of 100 g was applied to the end of the test piece in the shear direction at 60°C for 30 minutes.
• ⁇ in the following evaluation criteria means that the end of the test piece was subjected to a load of 100 g at 60 ° C. in the shear direction for 30 minutes, and then a load of 100 g was applied at 80 ° C. for 30 minutes. It means that it was 30 minutes or more and less than 60 minutes.
• ⁇ in the following evaluation criteria means that a load of 100 g is applied to the end of the test piece in the shear direction at 60 ° C. for 30 minutes, followed by a load of 100 g at 80 ° C.

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• 2022
  • 2022-02-24 JP JP2023502485A patent/JPWO2022181690A1/ja active Pending
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