Classifications

• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a resin composition containing an acrylic block copolymer.
• a resin composition containing an acrylic block copolymer having a polymer block containing an acrylic ester unit and a polymer block containing a methacrylic ester unit is used in various applications such as adhesives and soft materials due to its properties. is being considered for use in Among the above acrylic block copolymers, acrylic block copolymers containing an acrylic ester unit having an organic group having 1 to 3 carbon atoms in a polymer block containing an acrylic ester unit are resistant to plasticizers. Because of its excellent properties, for example, a laminate with a vinyl chloride resin or the like is being studied (for example, Patent Document 1).
• a resin composition containing an acrylic block copolymer when used as an adhesive or a soft material, it may be used in an environment where it comes into contact with the skin such as hands. When used in such an environment where the skin comes into contact with the skin, the resin composition may be contaminated with sebum, resulting in deterioration of physical properties of the resin composition.
• Oleic acid one of the main substances that make up sebum, is a low-molecular-weight organic compound similar to the plasticizer used in vinyl chloride, so it contains the acrylic block copolymer disclosed in Patent Document 1.
• the use of the resin composition is expected to solve the problem of contamination of the resin composition with sebum.
• an object of the present invention is to provide a resin composition containing an acrylic block copolymer that sufficiently suppresses contamination by substances contained in sebum, particularly oleic acid, and maintains flexibility.
• a polymer block containing an acrylate ester unit contains an acrylate unit having an organic group having 1 to 3 carbon atoms.
• the above objects are [1] 100 parts by mass of an acrylic block copolymer (I) having at least one polymer block (A1) containing a methacrylate ester unit and at least one polymer block (B1) containing an acrylic ester unit and an acrylic block copolymer (II) having at least one polymer block (A2) containing a methyl methacrylate unit and at least one polymer block (B2) containing an acrylic ester unit 15 to 400 mass
• a resin composition containing a part The content of the polymer block (A1) in the acrylic block copolymer (I) is 20% by mass or more,
• the polymer block (B1) of the acrylic block copolymer (I) has the general formula CH 2 ⁇ CH—COOR 1 (1) (in formula (1), R 1 represents an organic group having 1 to 3 carbon atoms).
• the acrylic block copolymer satisfies the following formulas (i) and (ii), (i) (H) x SP (A1) + (J) x SP (B1) - SP (C) > 1.20 (ii) ⁇ 0.80 ⁇ SP(A1) ⁇ SP(B1) ⁇ 0.43 (In the above formulas (i) and (ii), SP (A1) is the solubility parameter (cal/cm 3 ) 1/2 of the polymer block (A1), SP (B1) is the solubility parameter of the polymer block (B1), (cal/cm 3 ) 1/2 , SP (C) represents the solubility parameter (cal/cm 3 ) 1/2 of oleic acid, and (H) represents the acrylic block copolymerization of the polymer block (A1).
• the polymer block (B2) of the acrylic block copolymer (II) has the general formula CH 2 ⁇ CH—COOR 2 (2) (in formula (2), R 2 represents an organic group having 4 to 12 carbon atoms). and the content of the polymer block (A2) in the acrylic block copolymer (II) is less than 35% by mass.
• the resin composition of the present invention can sufficiently suppress contamination by substances contained in sebum, particularly oleic acid, and maintain flexibility.
• (meth)acrylic acid ester is a generic term for "methacrylic acid ester” and “acrylic acid ester”
• (meth)acrylic is a combination of “methacrylic” and “acrylic”. It is a generic term.
• the acrylic block copolymer (I) contained in the resin composition of the present invention comprises at least one polymer block (A1) containing methacrylate units and at least one polymer containing acrylic ester units.
• block (B1), and the acrylic acid ester unit contained in the polymer block (B1) is represented by the general formula CH 2 ⁇ CH—COOR 1 (1) (in formula (1), R 1 has 1 to Representing an organic group of 3) contains an acrylic acid ester (b1-1) unit.
• methacrylic acid esters that are constituent units of the polymer block (A1) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, Alkyl methacrylates such as cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and isobornyl methacrylate; Methacrylic acid esters having no functional groups other than alkyl methacrylates such as phenyl methacrylate and benzyl methacrylate; Methoxyethyl methacrylate, methacrylic acid alkoxyalkyl esters such as ethoxyethyl methacrylate, diethylaminoethyl
• alkyl methacrylate is preferred, and methyl methacrylate, ethyl methacrylate, and propyl methacrylate are more preferred, because they are economically available and the resulting polymer block (A1) has excellent durability and weather resistance. etc., methyl methacrylate is more preferable.
• the methacrylic acid ester unit of the polymer block (A1) may be obtained from only one type of methacrylic acid ester, or may be obtained from two or more types of methacrylic acid ester.
• the proportion of methacrylate units contained in the polymer block (A1) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more in the polymer block (A1).
• the polymer block (A1) may be composed of 100% by mass of methacrylic acid ester units, that is, composed only of methacrylic acid ester units.
• the polymer block (A1) may contain other monomer units within a range that does not impair the effects of the present invention.
• Such other monomers include, for example, acrylic acid esters; (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, vinyl monomers having a carboxyl group such as fumaric acid; (meth) acrylamide, Vinyl monomers having functional groups such as (meth)acrylonitrile, vinyl acetate, vinyl chloride and vinylidene chloride; Aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene and m-methylstyrene conjugated diene-based monomers such as butadiene and isoprene; olefin-based monomers such as ethylene, propylene, isobutene and octene; and lactone-based monomers such as ⁇ -caprolactone and valerolactone.
• Monomer units composed of these other monomers are usually in small amounts with respect to the total monomer units of the polymer block (A1), and other monomers contained in the polymer block (A1)
• the proportion of body units is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the glass transition temperature (Tg) of the polymer block (A1) is preferably 50 to 150°C, more preferably 60 to 140°C, even more preferably 70 to 130°C.
• the polymer block (A1) acts as a physical pseudo cross-linking point at the normal operating temperature of the resin composition of the present invention, A cohesive force is expressed in the composition, and the adhesive properties, durability, and heat resistance are excellent, and the hot-melt moldability is excellent.
• the glass transition temperature is the extrapolation start temperature of the curve obtained by DSC measurement.
• the acrylic block copolymer (I) may contain two or more polymer blocks (A1). In that case, the methacrylate ester units constituting the polymer blocks (A1) and The monomers can be the same or different.
• the weight average molecular weight (Mw) of the polymer block (A1) is not particularly limited, it is preferably in the range of 1,000 to 50,000, more preferably in the range of 4,000 to 20,000. .
• the Mw of the polymer block (A1) is 1,000 or more, the resulting acrylic block copolymer (I) tends to have a cohesive force.
• the Mw of the polymer block (A1) is 50,000 or less, the melt viscosity of the obtained acrylic block copolymer (I) does not become too high, and the acrylic block copolymer (I) and the moldability of the resulting resin composition containing the acrylic block copolymer (I).
• the weight average molecular weight (Mw) in this specification means the weight average molecular weight of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
• the polymer block (B1) contains acrylic acid ester units, and the acrylic acid ester units contained in the polymer block (B1) are represented by the general formula CH 2 ⁇ CH—COOR 1 (1) (in formula (1) , R 1 represents an organic group having 1 to 3 carbon atoms) (hereinafter simply referred to as acrylate (b1-1)) units.
• acrylic acid ester (b1-1) examples include acrylic acid esters having no functional groups such as methyl acrylate, ethyl acrylate, isopropyl acrylate, and n-propyl acrylate; 2-methoxyethyl acrylate, acrylic Acrylic acid esters having functional groups such as 2-hydroxyethyl acid, 2-aminoethyl acrylate, glycidyl acrylate, and the like can be mentioned.
• acrylic acid esters having no functional group are preferred, and methyl acrylate and ethyl acrylate are more preferred, from the viewpoint of increasing the stain resistance of the resulting resin composition against substances contained in sebum such as oleic acid. , and methyl acrylate are more preferred.
• acrylic acid esters (b1-1) may be used alone or in combination of two or more.
• acrylic ester (b1-1) units In addition to the acrylic ester (b1-1) units, the acrylic ester units constituting the polymer block (B1) have the general formula CH 2 ⁇ CH—COOR 2 (2) (wherein R 2 is the number of carbon atoms Representing 4 to 12 organic groups) (hereinafter simply referred to as acrylic ester (b1-2)) units are preferably contained.
• acrylic acid ester (b1-2) examples include n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, acrylic acrylic acid esters having no functional group such as 2-ethylhexyl acid, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; Acrylic acid esters having functional groups such as 2-ethoxyethyl acrylate, 2-(diethylamino)ethyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenoxyethyl acrylate can be mentioned.
• acrylic acid esters having no functional group are preferable because the phase separation between the polymer block (A1) and the polymer block (B1) becomes clearer. is more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are even more preferred.
• the flexibility and adhesive properties of the obtained resin composition at low temperatures 40 to 10 ° C.
• n-Butyl acrylate is more preferable from the viewpoint of excellent (tackiness, adhesion, etc.) and excellent durability.
• These acrylic acid esters (b1-2) may be used alone or in combination of two or more.
• the mass ratio (b1-1)/(b1-2) of the acrylic ester (b1-1) unit and the acrylic ester (b1-2) unit in the polymer block (B1) is 90/10 to 10/90. is preferably When the mass ratio is within the above range, stain resistance to substances contained in sebum such as oleic acid due to the acrylic ester (b1-1) unit and softness due to the acrylic ester (b1-2) unit Excellent compatibility with sexuality.
• the mass ratio (b1-1)/(b1-2) of the acrylic acid ester is 85/15 to 10/ It is preferably 90, more preferably 80/20 to 10/90, even more preferably 80/20 to 20/80.
• the mass ratio of the acrylic acid ester (b1-1) unit and the acrylic acid ester (b1-2) unit can be determined by 1 H-NMR measurement.
• the proportion of the acrylate (b1-1) units in the acrylate units of the polymer block (B1) is preferably 90% by mass or less, and 85% by mass or less in the polymer block (B1). and more preferably 80% by mass or less.
• the acrylic ester units contained in the polymer block (B1) consist of only acrylic ester (b1-1) units and acrylic ester (b1-2) units.
• the proportion of acrylic acid ester units in the polymer block (B1) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
• the polymer block (B1) is preferably composed of 100% by mass of acrylate units, that is, composed only of acrylate units.
• the polymer block (B1) may contain monomer units other than acrylic acid ester units within a range that does not impair the effects of the present invention.
• Other monomers constituting such units include, for example, methacrylic acid esters; (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid and other vinyl monomers having a carboxyl group; ) Vinyl monomers having functional groups such as acrylamide, (meth)acrylonitrile, vinyl acetate, vinyl chloride and vinylidene chloride; Aromatic vinyls such as styrene, ⁇ -methylstyrene, p-methylstyrene and m-methylstyrene conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene, propylene, isobutene and octene; and lactone monomers such as ⁇ -caprolactone and valerolactone.
• Monomer units composed of these other monomers are usually in small amounts with respect to the total monomer units of the polymer block (B1), and other monomers contained in the polymer block (B1)
• the proportion of body units is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• acrylic block copolymer (I) may contain two or more polymer blocks (B1).
• the combinations may be the same or different.
• the acrylic ester unit portion contained in the polymer block (B1) contains acrylic ester (b1-1) units and acrylic ester (b1-2) units
• the portion is It is composed of a copolymer of acrylic acid ester (b1-1) and acrylic acid ester (b1-2).
• the form of the copolymer may consist of a random copolymer, a block copolymer, or a graft copolymer of the acrylic acid ester (b1-1) and the acrylic acid ester (b1-2).
• a tapered block copolymer may be used, but a random copolymer is preferred.
• the acrylic block copolymer (I) contains two or more polymer blocks (B1)
• the polymer blocks (B1) may have the same or different structures.
• the glass transition temperature (Tg) of the polymer block (B1) is more preferably -50 to 55°C, more preferably -50 to 50°C, and further preferably -50 to 45°C. It is preferably -50 to 25°C, and more preferably -50°C to 25°C. When the glass transition temperature is within this range, there is a tendency to easily obtain a resin composition that is excellent in flexibility and durability at the temperature of use.
• the difference in glass transition temperature between the polymer block (A1) and the polymer block (B1) in the acrylic block copolymer (I) is preferably 50°C or higher, more preferably 70°C or higher.
• the acrylic block copolymer (I) has the general formula: when the polymer block (A1) is "A1"; (A1-B1) n (A1-B1) n -A1 A1-(A1-B1) n (A1-B1) n -Z (B1-A1) n -Z (Wherein, n is an integer of 1 to 30, Z represents a coupling site (coupling site after the coupling agent reacts with the polymer terminal to form a chemical bond)) is preferred.
• the value of n is preferably 1-15, more preferably 1-8, and even more preferably 1-4.
• the polymer block (A1) is bonded to both ends of the polymer block (B1).
• the following general formula: (A1-B1) n -A1 (A1-B1) m -Z (Wherein, n is an integer of 1 to 30, m is an integer of 2 to 30, Z represents a coupling site (coupling site after the coupling agent reacts with the polymer terminal to form a chemical bond) ) is preferably represented by The value of m is preferably 2-15, more preferably 2-8, even more preferably 2-4. The value of n is preferably 1-15, more preferably 1-8, and even more preferably 1-4. )
• linear block copolymers represented by (A1-B1) n , (A1-B1) n -A1, A1-(A1-B1) n are more preferable, represented by A1-B1
• a diblock copolymer represented by A1-B1-A1 and a triblock copolymer represented by A1-B1-A1 are more preferable, and a triblock copolymer represented by A1-B1-A1 is particularly preferable.
• These may be used individually by 1 type, and may be used in combination of 2 or more types.
• the content of the polymer block (A1) in the acrylic block copolymer (I) is 20% by mass or more, preferably 20 to 40% by mass.
• the content of the polymer block (A1) is 20% by mass or more, the cohesive force of the acrylic block copolymer (I) tends to increase, and the acrylic block copolymer (I) and the acrylic block described later
• a resin composition is produced from the copolymer (II)
• the content of the polymer block (A1) is 40% by mass or less, a resin composition with excellent flexibility tends to be obtained.
• the content of the polymer block (A1) in the acrylic block copolymer (I) is preferably 20 to 35% by mass, more preferably 25 to 31% by mass, from the viewpoint of obtaining a resin composition having excellent flexibility. is more preferable.
• the acrylic block copolymer (I) of the present invention must satisfy the following formulas (i) and (ii).
• SP (A1) is the solubility parameter (cal/cm 3 ) 1/2 of the polymer block (A1)
• SP (B1) is the solubility parameter of the polymer block (B1) ( cal/cm 3 ) 1/2
• SP (C) represents the solubility parameter (cal/cm 3 ) 1/2 of oleic acid
• (H) represents the acrylic block copolymer of the polymer block (A1).
• the mass ratio in (I) and (J) indicate the mass ratio of the polymer block (B1) in the acrylic block copolymer (I).
• the solubility parameter of each polymer block (A1) and (B1) is a value obtained by the Fedors estimation method.
• the solubility parameter (SP value ( ⁇ )) is defined as the square root of the cohesive energy density ( ⁇ E/V) calculated from the cohesive energy ( ⁇ E) and the molar molecular volume (V) of the solvent.
• Polymethyl acrylate (methyl acrylate units), poly n-butyl acrylate (n-butyl acrylate units), poly 2-ethylhexyl acrylate (2-ethylhexyl acrylate units) and poly methyl methacrylate (methyl methacrylate units ) are 11.30 (cal/cm 3 ) 1/2 , 10.20 (cal/cm 3 ) 1/2 and 9.50 (cal/cm 3 ) 1 , respectively. /2 and 10.50 (cal/cm 3 ) 1/2 . Also, SP(C) is 9.14 (cal/cm 3 ) 1/2 .
• the acrylic block copolymer (I) that satisfies the above formula (i) includes, for example, the ratio of the acrylic ester (b1-1) units in the acrylic ester units of the polymer block (B1), the polymer block (A1 ) can be obtained by adjusting the content of
• Equation (ii) The value of SP (A1) - SP (B1) in the above formula (ii) is the difference in solubility parameters between the polymer blocks (A1) and (B1) in the acrylic block copolymer (I), Equation (ii) shows that it is important that this difference be within a certain range. Since the difference in the solubility parameter is within a specific range, not only can it exhibit sufficient flexibility even when used in combination with the acrylic block copolymer (II) described later, but it can also be contained in sebum such as oleic acid.
• the acrylic block copolymer (I) that satisfies the above formula (ii) has, for example, a content of the acrylic ester (b1-1) unit in the acrylic ester unit of the polymer block (B1). Alternatively, it can be obtained by adjusting the content of the polymer block (A1).
• Mw of the acrylic block copolymer (I) is 30,000 to 300, 000, more preferably 40,000 to 250,000, even more preferably 50,000 to 220,000, even more preferably 60,000 to 200,000.
• Mw of the acrylic block copolymer (I) is 30,000 or more, the cohesive force of the acrylic block copolymer (I) increases, and the durability of the obtained resin composition tends to be more excellent.
• problems such as bleeding originating from the acrylic block copolymer (I) are less likely to occur on the surface of the molded article.
• the productivity and workability tend to be excellent.
• the compatibility with the acrylic block copolymer (II) described later tends to be good, and the transparency of the resin composition obtained tends to be more excellent, and the molded article produced from the resin composition Physical properties tend to be more stable.
• the acrylic block copolymer (I) preferably has a molecular weight distribution (Mw/Mn) of 1.0 to 1.5.
• Mw/Mn molecular weight distribution
• the molecular weight distribution of the acrylic block copolymer (I) is within the above range, the cohesive force of the acrylic block copolymer (I) can be easily increased, and mold contamination during molding of the obtained pellets can be suppressed. tends to be easy.
• the molecular weight distribution is more preferably 1.0 to 1.4, even more preferably 1.0 to 1.3.
• Mn means a number average molecular weight
• Mn number average molecular weight
• GPC gel permeation chromatography
• the acrylic block copolymer (II) contained in the resin composition of the present invention is a polymer different from the acrylic block copolymer (I) and has at least one polymer block containing a methyl methacrylate unit. (A2) and at least one polymer block (B2) containing an acrylate unit, the polymer block (B2) having the general formula CH 2 ⁇ CH—COOR 2 (2) (formula (2) in which R 2 represents an organic group having 4 to 12 carbon atoms), and the polymer block (A2) in the acrylic block copolymer (II) is less than 35% by mass.
• the acrylic block copolymer (II) in addition to the acrylic block copolymer (I) in the resin composition of the present invention, contamination by substances contained in sebum, particularly oleic acid, is sufficiently suppressed. It is possible to obtain a resin composition that not only can be used for sintering, but also has excellent flexibility.
• the proportion of the methyl methacrylate unit contained in the polymer block (A2) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more in the polymer block (A2). Further, the polymer block (A2) is also preferably composed of 100% by mass of methyl methacrylate units, that is, composed only of methyl methacrylate units.
• the polymer block (A2) may contain monomer units other than methyl methacrylate as long as the effects of the present invention are not impaired.
• monomers include methacrylic acid esters other than methyl methacrylate, acrylic acid esters; (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, etc.
• Monomer vinyl-based monomer having a functional group such as (meth)acrylamide, (meth)acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride; styrene, ⁇ -methylstyrene, p-methylstyrene, m-methyl Aromatic vinyl monomers such as styrene; Conjugated diene monomers such as butadiene and isoprene; Olefin monomers such as ethylene, propylene, isobutene and octene; Lactone monomers such as ⁇ -caprolactone and valerolactone A body etc. are mentioned.
• Monomer units composed of these other monomers are usually a small amount with respect to the total monomer units of the polymer block (A2), and other monomers contained in the polymer block (A2)
• the proportion of body units is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the glass transition temperature (Tg) of the polymer block (A2) is preferably 50 to 150°C, more preferably 70 to 140°C, even more preferably 80 to 130°C.
• Tg glass transition temperature
• the glass transition temperature of the polymer block (A2) is within the above range, there is a tendency that when stored as pellets, stickiness at high temperatures (for example, 50° C.) is reduced (stickiness resistance is improved).
• the acrylic block copolymer (II) may contain two or more polymer blocks (A2).
• methyl methacrylate units constituting the polymer blocks (A2) and other The monomers can be the same or different.
• Mw of the polymer block (A2) is not particularly limited, it is preferably in the range of 1,000 to 50,000, more preferably in the range of 4,000 to 20,000. If the Mw of the polymer block (A2) is less than 1,000, the resulting acrylic block copolymer (II) may lack cohesion. Further, when the Mw of the polymer block (A2) is more than 50,000, the melt viscosity of the obtained acrylic block copolymer (II) increases, and the productivity of the acrylic block copolymer (II) increases. Otherwise, the moldability of pellets containing the obtained resin composition may be inferior.
• the polymer block (B2) contains acrylic acid ester units, and the acrylic acid ester units contained in the polymer block (B2) are represented by the general formula CH 2 ⁇ CH—COOR 2 (2) (wherein R 2 represents an organic group having 4 to 12 carbon atoms) (hereinafter simply referred to as acrylate (b2-2)) units.
• acrylic ester (b2-2) are the same as the acrylic ester (b1-2) that can be one of the constituent units of the polymer block (B1) of the acrylic block copolymer (I).
• acrylic acid esters (b2-2) acrylic acid esters having no functional group are preferable because the phase separation between the polymer block (A2) and the polymer block (B2) becomes clearer.
• Alkyl acrylates having 4 to 12 alkyl groups are more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are even more preferred. Further, n-butyl acrylate is more preferable because the resin composition of the present invention tends to be more flexible and a resin composition having excellent durability tends to be obtained.
• the acrylic ester (b2-2) units constituting the acrylic ester units contained in the polymer block (B2) may be obtained from only one type of acrylic ester (b2-2). , two or more acrylic acid esters (b2-2).
• the proportion of acrylic acid ester units contained in the polymer block (B2) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more in the polymer block (B2). Further, the polymer block (B2) may be composed of 100% by mass of acrylate units, that is, composed only of acrylate units.
• the acrylate unit contained in the polymer block (B2) has the general formula CH 2 ⁇ CH—COOR 1 (1) (wherein R 1 represents an organic group having 1 to 3 carbon atoms). It is a preferred form that the acrylate (b2-1) represented by (hereinafter simply referred to as acrylate (b2-1)) unit is not included.
• Specific examples of the acrylic acid ester (b2-1) are the same as the acrylic acid ester (b1-1) constituting the polymer block (B1) of the acrylic block copolymer (I). Since the acrylic acid ester (b2-1) unit is not contained in the polymer block (B2), a resin composition having excellent flexibility can be obtained.
• the acrylic ester unit contained in the polymer block (B2) is composed only of the acrylic ester (b2-2) unit.
• the acrylic ester units of the polymer block (B2) consist only of acrylic ester (b2-2) units, a resin composition having excellent flexibility can be obtained.
• the polymer block (B2) may contain monomer units other than acrylic acid ester units within a range that does not impair the effects of the present invention. Specific examples of such other monomers are the same as other monomers that can be a constituent unit of the polymer block (B1) of the acrylic block copolymer (I). Monomer units composed of these other monomers are usually a small amount with respect to the total monomer units of the polymer block (B2), and other monomers contained in the polymer block (B2) The proportion of body units is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the glass transition temperature of the polymer block (B2) is preferably -100 to 40°C, more preferably -80 to 35°C, even more preferably -70 to 30°C.
• the flexibility is excellent even in a low temperature range.
• n-butyl acrylate, 2-ethylhexyl acrylate, n- Octyl is preferred.
• acrylic block copolymer (II) may contain two or more polymer blocks (B2).
• the combinations may be the same or different.
• the difference in glass transition temperature between the polymer block (A2) and the polymer block (B2) in the acrylic block copolymer (II) is preferably 70°C or higher, more preferably 100°C or higher.
• the acrylic block copolymer (II) has the general formula: when the polymer block (A2) is "A2"; (A2-B2) i (A2-B2) i -A2 A2-(A2-B2) i (A2-B2) i -Z (B2-A2) i -Z (Wherein, i is an integer of 1 to 30, Z is a coupling site (coupling site after the coupling agent reacts with the polymer terminal to form a chemical bond)). is preferred.
• the value of i is preferably 1-15, more preferably 1-8, and even more preferably 1-4.
• the polymer block (A2) is bonded to both ends of the polymer block (B2).
• the following general formula: (A2-B2) i -A2 (A2-B2) k -Z (Wherein, i is an integer of 1 to 30, k is an integer of 2 to 30, Z represents a coupling site (coupling site after the coupling agent reacts with the polymer end to form a chemical bond) ) is preferably represented by The value of k is preferably 2-15, more preferably 2-8, even more preferably 2-4. The value of i is preferably 1-15, more preferably 1-8, and even more preferably 1-4. )
• linear block copolymers represented by (A2-B2) i , (A2-B2) i -A2, and A2-(A2-B2) i are more preferable, represented by A2-B2
• a diblock copolymer represented by A2-B2-A2 and a triblock copolymer represented by A2-B2-A2 are more preferable, and a triblock copolymer represented by A2-B2-A2 is particularly preferable.
• These may be used individually by 1 type, and may be used in combination of 2 or more types.
• the content of the polymer block (A2) in the acrylic block copolymer (II) is less than 35% by mass.
• the acrylic block copolymer (II) becomes flexible, and the resin composition obtained by mixing with the acrylic block copolymer (I). flexibility.
• the content of the polymer block (A2) in the acrylic block copolymer (II) is preferably less than 33% by mass, more preferably 32% by mass, because a resin composition having excellent flexibility can be obtained more easily. It is more preferably less than.
• the content of the polymer block (A2) is preferably 3% by mass or more.
• the Mw of the acrylic block copolymer (II) is 30,000 to 300,000. preferably 30,000 to 200,000, even more preferably 40,000 to 180,000, even more preferably 50,000 to 160,000.
• the Mw of the acrylic block copolymer (II) is 30,000 or more, the cohesive force of the acrylic block copolymer (II) increases, and the durability of the obtained resin composition tends to be more excellent.
• problems such as bleeding originating from the acrylic block copolymer (II) are less likely to occur on the surface of the molded article.
• the productivity and workability tend to be excellent.
• the compatibility with the acrylic block copolymer (I) described above tends to be good, and the resulting resin composition tends to be more excellent in transparency, and a molded article produced from the resin composition. Physical properties tend to be more stable.
• the acrylic block copolymer (II) preferably has a molecular weight distribution (Mw/Mn) of 1.0 to 1.5.
• Mw/Mn molecular weight distribution
• the molecular weight distribution of the acrylic block copolymer (II) is within the above range, the cohesive force of the acrylic block copolymer (II) can be easily increased, and contamination of equipment during processing of the resulting resin composition can be suppressed. tends to be easier.
• the molecular weight distribution is more preferably 1.0 to 1.4, even more preferably 1.0 to 1.3.
• the MFR of the acrylic block copolymer (II) under conditions of 230°C and a load of 3.8 kg is preferably 20 g/10 minutes or more, more preferably 30 g/10 minutes or more.
• MFR is at least the above lower limit, miscibility with the acrylic block copolymer (I) is more excellent, and good compatibility and excellent transparency tend to be obtained. If the MFR is too high, the kneadability during processing tends to be insufficient due to the low melt viscosity. It is more preferable to have When the MFR is equal to or less than the above upper limit, there is a tendency that melt-kneading can be easily performed.
• the method for producing acrylic block copolymer (I) and acrylic block copolymer (II) is not particularly limited, and these acrylic block copolymers can be produced by a production method according to known methods.
• a method for obtaining a block copolymer with a narrow molecular weight distribution a method of living polymerization of a monomer that is a constituent unit is employed.
• Examples of such a living polymerization method include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see, for example, JP-A-11-335432), and an alkali metal compound using an organic alkali metal compound as a polymerization initiator.
• a method of living anionic polymerization in the presence of mineral acid salts such as alkaline earth metal salts see, for example, JP-B-7-25859
• an organic alkali metal compound as a polymerization initiator and living in the presence of an organic aluminum compound examples thereof include an anionic polymerization method (see, for example, JP-A-6-93060) and an atom transfer radical polymerization method (ATRP) (see, for example, Macromol. Chem. Phys., 2000, 201, p.
• the method of living anion polymerization in the presence of an organoaluminum compound has less deactivation during polymerization, so less homopolymer is mixed in, and the obtained block copolymer has high transparency.
• the polymerization conversion rate of the monomer is high, the amount of residual monomer in the block copolymer is small, and the generation of air bubbles can be suppressed when producing pellets containing the acrylic block copolymer.
• the molecular structure of the polymer block composed of the methacrylic acid alkyl ester units becomes highly syndiotactic, which has the effect of increasing the durability of the resulting resin composition containing the acrylic block copolymer.
• the acrylic block copolymer is preferably produced by a method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound.
• Examples of the living anionic polymerization method in the presence of the organoaluminum compound include an organolithium compound and the following general formula (3) AlR3R4R5 ( 3 ) (In formula (3), R 3 , R 4 and R 5 are each independently an optionally substituted alkyl group, an optionally substituted cycloalkyl group, a substituted aryl group, optionally substituted aralkyl group, optionally substituted alkoxy group, optionally substituted aryloxy group or N,N-disubstituted amino group or R 3 is any of the groups described above, and R 4 and R 5 together form an arylenedioxy group which may have a substituent.
• R 3 , R 4 and R 5 are each independently an optionally substituted alkyl group, an optionally substituted cycloalkyl group, a substituted aryl group, optionally substituted aralkyl group, optionally substituted alkoxy group, optionally substituted aryloxy group or N,N-d
• Ether compounds such as dimethyl ether, dimethoxyethane, diethoxyethane, 12-crown-4, etc.; triethylamine, N,N,N',N'-tetramethyl Nitrogen-containing compounds such as ethylenediamine, N,N,N',N'',N'-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, pyridine, and 2,2'-dipyridyl is further added to polymerize the (meth)acrylic acid ester.
• Examples of the organic lithium compound include alkyllithium or alkyldilithium such as n-butyllithium, sec-butyllithium and tetramethylenedilithium; aryllithium or aryldilithium such as phenyllithium and xylyllithium; benzyllithium; Examples include aralkyllithium or aralkyldilithium such as dilithium produced by the reaction of diisopropenylbenzene and butyllithium; lithium amides such as lithium diisopropylamide; and lithium alkoxides such as methoxylithium.
• alkyllithium or alkyldilithium such as n-butyllithium, sec-butyllithium and tetramethylenedilithium
• aryllithium or aryldilithium such as phenyllithium and xylyllithium
• benzyllithium examples include aralkyllithium or
• organoaluminum compound represented by the general formula (3) isobutylbis(2,6-di-tert-butyl-4-methyl phenoxy)aluminum, isobutylbis(2,6-di-tert-butylphenoxy)aluminum, isobutyl[2,2'-methylenebis(4-methyl-6-tert-butylphenoxy)]aluminum and the like are preferred.
• the resin composition of the present invention contains 15 to 400 parts by mass of the acrylic block copolymer (II) with respect to 100 parts by mass of the acrylic block copolymer (I).
• the content of the acrylic block copolymer (II) with respect to 100 parts by mass of the acrylic block copolymer (I) is less than 15 parts by mass, the flexibility of the resulting resin composition not sexual enough.
• the content of the acrylic block copolymer (II) with respect to 100 parts by mass of the acrylic block copolymer (I) exceeds 400 parts by mass, the resulting resin composition will be contaminated with substances contained in sebum.
• the acrylic block copolymer in the resin composition of the present invention The content of the acrylic block copolymer (II) with respect to 100 parts by mass of (I) is preferably 15 to 300 parts by mass, more preferably 20 to 200 parts by mass.
• the total content of acrylic block copolymer (I) and acrylic block copolymer (II) contained in the resin composition of the present invention is preferably 80% by mass or more, and is 90% by mass or more. more preferably 95% by mass or more, and may be 100% by mass.
• the resin composition of the present invention contains other polymers, tackifying resins, softeners, plasticizers, heat stabilizers, light stabilizers, antistatic agents, flame retardants, foaming agents, as long as the effects of the present invention are not impaired. , colorants, dyes, refractive index modifiers, fillers, hardeners, lubricants, anti-sticking agents, anti-termites, and anti-mouse agents.
• One of these other polymers and additives may be contained, or two or more of them may be contained.
• acrylic resins such as polymethyl methacrylate and (meth)acrylic acid ester polymers or copolymers
• polyethylene ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly -Olefin resins such as 4-methylpentene-1 and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers, high impact polystyrene, AS resins, ABS resins, AES resins, AAS resins, ACS resins, Styrene resins such as MBS resin; styrene-methyl methacrylate copolymer; styrene-methyl methacrylate-maleic anhydride copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; nylon 6, nylon 66, Polyamide such as polyamide elastomer; Polycarbonate
• polymethyl methacrylate, (meth)acrylic acid ester polymer or copolymer , ethylene-vinyl acetate copolymer, AS resin, styrene-methyl methacrylate-maleic anhydride copolymer, polylactic acid, polyvinylidene fluoride are preferred, polymethyl methacrylate, (meth) acrylic acid ester copolymer, styrene -methyl methacrylate-maleic anhydride copolymer is more preferred.
• Examples of the (meth)acrylate polymer or copolymer include polymethyl acrylate, n-butyl polyacrylate, 2-ethylhexyl polyacrylate, random copolymers of methyl methacrylate and methyl acrylate, Random copolymers of methyl methacrylate and n-butyl acrylate, diblock copolymers consisting of at least one polymer block consisting of methacrylate ester units and at least one polymer block consisting of acrylic ester units and triblock copolymers (however, the above diblock copolymers and triblocks do not include the acrylic block copolymer (I) and the acrylic block copolymer (II) of the present invention). do not have.).
• the resin composition of the present invention contains a tackifying resin
• pressure-sensitive adhesiveness tackiness
• the resin composition is used as an adhesive agent, the tackiness, adhesive strength and holding power can be easily adjusted.
• the tackifying resin include natural resins such as rosin-based resins and terpene-based resins; petroleum resins, hydrogenated (hereinafter sometimes referred to as "hydrogenated") petroleum resins, styrene-based resins, and coumarone-indene-based resins.
• synthetic resins such as phenol-based resins and xylene-based resins.
• the content thereof is, from the viewpoint of adhesive strength and durability, a total of 100 parts by mass of the acrylic block copolymer (I) and the acrylic block copolymer (II). It is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, even more preferably 5 to 50 parts by mass, particularly preferably 5 to 40 parts by mass, and 5 ⁇ 35 parts by weight is most preferred.
• rosin-based resin examples include rosins such as gum rosin, tall oil rosin, and wood rosin; modified rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin; Rosin ester etc. are mentioned.
• specific examples of the rosins include Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, and Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries, Ltd.). be done.
• terpene-based resin examples include terpene resins mainly composed of ⁇ -pinene, ⁇ -pinene, dipentene, etc., aromatic modified terpene resins, hydrogenated terpene resins, and terpene phenol resins.
• terpene resins mainly composed of ⁇ -pinene, ⁇ -pinene, dipentene, etc. aromatic modified terpene resins, hydrogenated terpene resins, and terpene phenol resins.
• a specific example of the terpene-based resin is Tamanol 901 (manufactured by Arakawa Chemical Industries, Ltd.).
• Examples of the (hydrogenated) petroleum resins include (hydrogenated) aliphatic (C5) petroleum resins, ( hydrogenated) aromatic ( C9 ) petroleum resins, (hydrogenated) copolymer ( C5/ C9 ) petroleum resins, (hydrogenated) dicyclopentadiene petroleum resins, alicyclic saturated hydrocarbon resins, and the like.
• styrene resin examples include poly ⁇ -methylstyrene, ⁇ -methylstyrene/styrene copolymer, styrene monomer/aliphatic monomer copolymer, styrene monomer/ ⁇ -methyl Examples include styrene/aliphatic monomer copolymers, styrene monomer copolymers, styrene monomer/aromatic monomer copolymers, and the like. Specific examples of the styrene resin include FTR6000 series and FTR7000 series (manufactured by Mitsui Chemicals, Inc.).
• rosin-based resins rosin-based resins, terpene-based resins, (hydrogenated) petroleum resins and styrene-based resins are preferable in terms of expressing high adhesive strength, and rosin-based resins are preferable from the viewpoint of improving adhesiveness.
• Disproportionated or hydrogenated rosins purified by operations such as distillation, recrystallization, and extraction are more preferable from the viewpoint of suppressing deterioration in light resistance, coloration, and generation of bubbles due to impurities. These may be used alone or in combination of two or more.
• the softening point of the tackifier resin is preferably 50 to 150° C. from the viewpoint of exhibiting high adhesive strength.
• plasticizer examples include phthalates such as dibutyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di-n-decyl phthalate and diisodecyl phthalate, di-2-ethylhexyl sebacate, Sebacate esters such as di-n-butyl sebacate, azelate esters such as di-2-ethylhexyl azelate, fatty acid esters such as adipate esters such as di-2-ethylhexyl adipate and di-n-octyl adipate paraffins such as chlorinated paraffin; glycols such as polypropylene glycol; epoxy polymer plasticizers such as epoxidized soybean oil and epoxidized linseed oil; phosphate esters such as trioctyl phosphate and triphenyl phosphate; Phosphites such as triphenyl
• the filler examples include inorganic fibers and organic fibers such as glass fiber and carbon fiber; and inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate and magnesium carbonate.
• inorganic fibers and organic fibers are contained, durability is imparted to the resulting resin composition.
• inorganic filler is contained, heat resistance and weather resistance are imparted to the resulting resin composition.
• titanium oxide when titanium oxide is contained, light shielding properties are likely to be imparted to the resulting resin composition.
• the amount of titanium oxide added in the resin composition is preferably 20 to 250 parts by mass, more preferably 100 parts by mass in total of the acrylic block copolymer (I) and the acrylic block copolymer (II). is 30 to 150 parts by mass.
• the resin composition of the present invention When used together with a curing agent, it can be suitably used as a layer made of a UV-curable resin composition. Moreover, it can be suitably used as a UV-curing pressure-sensitive adhesive.
• the curing agent include photocuring agents such as UV curing agents, heat curing agents, and the like, and examples thereof include benzoins, benzoin ethers, benzophenones, anthraquinones, benzils, acetophenones, and diacetyls. .
• Curing agents may be used alone or in combination of two or more.
• monomers such as (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, styrene derivatives;
• An oligomer or the like containing a mer as a constituent may be further added.
• a cross-linking agent comprising a bifunctional or higher monomer or oligomer may be added.
• the resin composition of the present invention contains the acrylic block copolymer (I) and the acrylic block copolymer (II), it has excellent weather resistance.
• a light stabilizer By containing a light stabilizer, it is possible to develop even higher weather resistance.
• antioxidants include phenolic antioxidants, phosphorus antioxidants, and the like.
• ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
• Light stabilizers include hindered amine light stabilizers and the like. These may be contained individually by 1 type in the resin composition of this invention, and may be contained 2 or more types. Among them, it is a preferable embodiment that the molded article contains all of the antioxidant, the ultraviolet absorber, and the light stabilizer.
• the amount of each of the resin compositions of the present invention added is preferably 0.01 to 1.0 with respect to a total of 100 parts by mass of the acrylic block copolymer (I) and the acrylic block copolymer (II). parts by mass, more preferably 0.03 to 0.60 parts by mass.
• the method for producing the resin composition of the present invention is not particularly limited. , by mixing at a temperature within the range of 100-300°C. Moreover, after dissolving and mixing each component in an organic solvent, you may manufacture by distilling off this organic solvent.
• the resulting composition can be laminated with a layer made of a resin composition containing a plasticizer, which will be described later, after being melted by heat.
• the obtained resin composition can be used, for example, as a hot-melt pressure-sensitive adhesive by heating and melting.
• the plasticizing is performed before evaporating the organic solvent.
• the organic solvent can be distilled off and laminated on the layer of the resin composition.
• the resin composition is used as an adhesive, the components are dissolved in an organic solvent and mixed, and then the organic solvent is distilled off to produce the adhesive. It can be used as a pressure-sensitive adhesive by applying it to an adherend before distilling off the organic solvent, then distilling off the organic solvent and performing heat-sensitive adhesion.
• the melt viscosity is low from the viewpoint of workability and handling.
• the melt viscosity is preferably 50,000 mPa ⁇ s or less, more preferably 30,000 mPa ⁇ s or less.
• acrylic block copolymer (I) and the acrylic block copolymer (II) other polymers or additives may be added as necessary as raw materials for the resin composition of the present invention.
• the ingredients contained in the raw materials are contained, in order to enhance the dispersibility of each component contained in the raw materials, it is recommended to melt and mix these raw materials once using the above-described apparatus or the like.
• it improves the kneadability and compatibility between the acrylic block copolymer (I) and the acrylic block copolymer (II) contained in the resin composition of the present invention and the optional components.
• a twin-screw extruder From a point of view, it is preferable to use a twin-screw extruder.
• the temperature during mixing may be appropriately adjusted depending on the acrylic block copolymer (I) and the acrylic block copolymer (II) and the components added as necessary, and is usually 110°C to 300°C. It is good to mix at the temperature within the range.
• the resin composition of the present invention thus obtained can be formed at a sufficiently low temperature and can be heat-sensitive adhesive processed or hot-melt coated at a sufficiently low temperature. Temperatures of ⁇ 180°C allow these processes.
• a cylindrical test piece having a thickness of 1 mm and a diameter of 25 mm obtained by molding the resin composition is immersed in oleic acid, and the mass change rate [(immersion The mass of the test piece after immersion) ⁇ (the mass of the test piece before immersion)]/(the mass of the test piece before immersion) ⁇ 100 is preferably 200% or less.
• the mass change rate is more preferably 180% or less, and even more preferably 160% or less.
• the resin composition of the present invention can be used as a molded article by molding using a generally used molding method.
• the molding method include extrusion molding, injection molding, compression molding, blow molding, calender molding, vacuum molding, and other melt molding processing methods involving heating and melting, and solution casting methods.
• the melt molding method is preferable from the viewpoint of the handleability of the resin composition of the present invention.
• a molded article having an arbitrary shape is obtained.
• the hardness of the molded article is preferably 7.5 to 75, more preferably 8 to 65, even more preferably 10 to 60, from the viewpoint of physical properties and flexibility as a molded article.
• the raw material of the molded article (for example, pellets made of the resin composition of the present invention) is extruded or injection molded to contain the resin composition of the present invention.
• Monolayers can be produced.
• Extrusion molding methods include, for example, the T-die method and the inflation method, and among these, the T-die method is preferred.
• the resin composition of the present invention for example, pellets made of the resin composition of the present invention
• the raw material of the molded article is heated and melted and extruded from a T-die to obtain a single layer body.
• the resin composition of the present invention (for example, pellets of the resin composition of the present invention), which is the raw material of the molded article, is applied to the base layer.
• the resin composition of the present invention for example, pellets of the resin composition of the present invention
• the base layer is applied to the base layer.
• extrusion molding a laminate having a polymer layer containing acrylic block copolymer (I) and acrylic block copolymer (II) and a substrate layer can be produced.
• Extrusion methods include, for example, the T-die method and the inflation method, and among these, the T-die method is preferred.
• the laminate can be produced without using a solvent, and can be produced with relatively simple manufacturing equipment. By producing the laminate by extrusion molding, the production process can be simplified and the production cost of the laminate can be reduced.
• the resin composition of the present invention for example, pellets of the resin composition of the present invention
• the substrate is removed from the T-die.
• the co-extrusion molding method which is another example of the T-die method
• both the raw material of the layer containing the resin composition and the raw material of the base layer are heated and melted, and extruded at the same time.
• a laminate containing a layer containing the resin composition of the present invention and a substrate layer can be produced.
• the resin composition of the present invention is preferably extruded from a die at a temperature of 140 to 260°C in order to obtain good adhesion to the substrate layer.
• examples of the base material layer include films and sheets of synthetic polymer compounds, metal foils, papers, cellophane, nonwoven fabrics, woven fabrics, and the like.
• synthetic polymer compounds include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polyamide, polyvinyl alcohol, polycarbonate, cycloolefin resin, styrene-methyl methacrylate copolymer, polyvinyl chloride, ethylene-vinyl acetate copolymer, Examples include, but are not limited to, polymers, polymethyl methacrylate, polyethylene, polypropylene, mixtures of two or more of these polymers, and the like.
• the synthetic polymer compound may be a copolymer obtained by copolymerizing various monomers. These films and sheets may be vapor-deposited with aluminum, alumina, or silicon dioxide. In addition, the films and sheets of these synthetic polymer compounds may be further printed with urethane ink or the like.
• Examples of metal foil include aluminum foil and copper foil
• examples of paper include kraft paper, high-quality paper, and glassine paper.
• Examples of nonwoven fabrics include nonwoven fabrics made of aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, polyester fiber, polyolefin fiber, rayon fiber, and the like.
• Examples of woven fabrics include woven fabrics made of aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, polyester fiber, polyolefin fiber, rayon fiber, and the like.
• the structure of the laminate includes, for example, a two-layer structure with a layer containing the resin composition of the present invention and a base layer, a three-layer structure with two base layers and a layer containing the resin composition of the present invention ( base layer/resin composition layer/base layer), two different layers containing the base layer and the resin composition of the present invention, the resin composition layer (a), the resin composition layer (b), and the base layer A four-layer configuration (base material layer / resin composition layer (a) / resin composition layer (b) / base layer), a base layer and a layer (a) containing the resin composition of the present invention and the A four-layer structure of a layer (c) containing a resin composition and a base layer (base layer/resin composition layer (a)/resin composition layer (c)/base layer), three base layers and Examples include, but are not limited to, a five-layer structure (base material layer/resin composition layer/base material layer/resin composition layer/base material layer) with two layers
• the thickness ratio of the substrate layer of the laminate and the layer containing the resin composition of the present invention is not particularly limited. /1000 to 1000/1, more preferably 1/200 to 200/1.
• the adhesive surface of the substrate layer which is in contact with the layer containing the resin composition of the present invention, may be oxidized with air or ozone gas.
• the adhesive surface of the substrate layer may be subjected to known surface treatments such as anchor coating agent treatment, corona discharge treatment, flame treatment and plasma treatment.
• an anchor layer may be formed on the surface of at least one of the resin composition layer and the substrate layer using an adhesive resin or the like.
• resins used for such anchor layers include ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ionomers, block copolymers (for example, styrene-based triblock copolymers such as SIS and SBS, and diblock copolymers, etc.), ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and the like.
• the anchor layer may be one layer, or two or more layers.
• the method of forming the anchor layer is not particularly limited.
• a method of forming an anchor layer on the surface of the substrate layer by using a T-die or the like can be mentioned.
• the co-extrusion molding method which is an example of the T-die method, may be either a feed block method or a multi-manifold method.
• a laminate of two kinds and two layers, a laminate of three kinds and three layers having an intermediate layer between the substrate layer and the resin composition layer, and the like can be produced.
• Suitable examples of the synthetic polymer compound is polyolefin.
• polyolefin materials include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene- ⁇ olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, Ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, polypropylene (homopolymer, random copolymer, block copolymer) and the like.
• polyolefin-based materials may be used alone, or may be used as a mixture or composition in any combination.
• block copolymer polypropylene is preferable as the material for the base material layer.
• the base material layer is not limited to a single layer, and may have a plurality of base material layers.
• the total thickness of the substrate layer consisting of a single layer or multiple layers is preferably 20 ⁇ m or more and 100 ⁇ m or less, for example.
• the laminate may have an intermediate layer.
• Resins that can be used as the intermediate layer include, for example, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ionomers, block copolymers (for example, styrene-based triblock copolymers such as SIS and SBS, and di- block copolymers, etc.), ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and the like.
• the intermediate layer may be one layer, or two or more layers, and can be formed by co-extrusion simultaneously with the base layer and the layer containing the resin composition of the present invention.
• the resin composition of the present invention (for example, pellets of the resin composition of the present invention) is injection molded.
• a multilayer body having a layer (Z) containing the resin composition of the present invention and a polymer layer (Y) made of a material other than the resin composition of the present invention can be produced.
• injection molding methods include two-color molding and insert molding.
• Polymers constituting the polymer layer (Y) (hereinafter also referred to as layer (Y)) made of materials other than the resin composition of the present invention include, for example, polymethyl methacrylate and (meth)acrylic Acrylic resins such as acid ester copolymers; olefin resins such as polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; Styrene resins such as styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; styrene-methyl methacrylate copolymer; polyethylene terephthalate, amorphous Polyethylene terephthalate (PET-G), polybutylene terephthalate, polyester resins such as polylactic acid; nylon 6, nylon 66, poly
• Examples of the layer (Y) include a layer (YI) containing a polar resin.
• Examples of the polar resin include acrylic resins such as polymethyl methacrylate and (meth)acrylate copolymer; polystyrene, styrene-maleic anhydride copolymer, high-impact polystyrene, AS resin, ABS resin, and AES.
• Styrene resins such as resins, AAS resins, ACS resins, and MBS resins; styrene-methyl methacrylate copolymers; polyester resins such as polyethylene terephthalate, amorphous polyethylene terephthalate (PET-G), polybutylene terephthalate, and polylactic acid; Polyamide such as nylon 6, nylon 66, polyamide elastomer; Polycarbonate; Polyvinyl chloride; Polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl alcohol copolymer; Polyacetal; modified resin; acrylic rubber; silicone rubber and the like.
• PET-G amorphous polyethylene terephthalate
• Polybutylene terephthalate polylactic acid
• Polyamide such as nylon 6, nylon 66, polyamide elastomer
• Polycarbonate Polyvinyl chloride; Polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl alcohol copolymer; Poly
• the layer (Z) and the layer (YI) are preferably adjacent to each other.
• the multilayer body has a layer (Z) that is excellent in low tack, transparency, flexibility, and impact absorption. Even when a highly rigid polar resin is used for the layer (YI) containing a polar resin, it is possible to have the properties of being excellent in both flexibility and impact absorption.
• the thickness of the layer (Z) and the layer (Y) constituting the multilayer body is not particularly limited, but from the viewpoint of the molded body being excellent in flexibility and impact absorption, the thickness of the layer (Z) is 0.1 to 10 mm. is preferred, 0.3 to 5 mm is more preferred, 0.5 to 3 mm is even more preferred, 0.7 to 2 mm, and may be 1 to 1.5 mm.
• the thickness of layer (Y) is preferably 0.3 to 10 mm, more preferably 0.5 to 5 mm, even more preferably 1 to 3 mm.
• Specific methods for producing the multilayer body include, for example, a method of separately forming the layer (Z) and the layer (Y) in advance and laminating them (method 1); A method of forming a layer (Z) by disposing the pellets of the present invention in a molten state on a layer (Y) placed thereon (Method 2); and a method of forming the layer (Y) (Method 3).
• methods 2 and 3 are preferable because the adhesive strength between the layer (Z) and the layer (Y) is improved, and method 2 is more preferable because the desired molded article can be obtained easily. .
• the resin composition of the present invention typically pellets of the resin composition of the present invention
• the layer (Z) by injection molding. It is more preferable to employ insert molding in which the layer (Y) is placed in a mold and then the resin composition of the present invention in a molten state is injected.
• Shapes of molded articles obtained from the resin composition include various shapes such as pellets, sheets, plates, pipes, tubes, belts, hoses, rods, and granules.
• automotive interior and exterior parts include car audio panels, instrument panels, dashboards, airbag covers, bumper parts, body panels, weather strips, grommets, glass run channels, rack and pinion boots, and suspension boots. , constant velocity joint boots, side moldings, mat guards, emblems, leather seats, floor mats, armrests, steering wheel covers, belt line moldings, flush mounts, gears, knobs, etc.
• liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation systems, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, displays for OA equipment, displays for AV equipment, electroluminescence display elements, touch panels, etc. can also be used for
• interior and exterior building materials such as curtain walls, roofing materials, roofing materials, window materials, rain gutters, exteriors, wall materials, flooring materials, It can be suitably applied to building materials, coated steel plates, coated plywood, sealing packings for doors and window frames, and the like.
• anti-vibration rubber, mats, seats, cushions, dampers, pads, mount rubber, and other anti-vibration rubber and damping materials materials for footwear such as sports shoes and fashion sandals; Home appliance parts; grips for scissors, screwdrivers, toothbrushes, pens, cameras, ski poles, etc.; office machine parts, such as copier feed rollers and take-up rollers; furniture, such as sofas and chair seats; switch covers, casters, stoppers, feet Parts such as rubbers and earphones; sporting goods such as swimming goggles, snorkels, ski boots, snowboard boots, skis/snowboards, golf ball covers; industrial materials such as conveyor belts, electric belts, pelletizer rolls; paper diapers, poultice materials Elastic members for sanitary materials such as bandages; Band applications such as hair bands, wrist bands, watch bands, and eyeglass bands; Food packaging materials such as food wrap films; Medical devices such as infusion bags, syringes, catheters, and rolling tubes; It can be effectively used for a
• the laminate which is one type of the molded article of the present invention, can be used for various purposes.
• surface protection masking, wrapping/packaging, office use, labeling, decoration/indication, bookbinding, dicing tape, medical/hygiene, laminated glass, shatterproof glass, electrical insulation
• Examples include adhesive tapes and adhesive films for holding and fixing electronic devices, manufacturing semiconductors, optical display films, adhesive optical films, electromagnetic wave shields, and sealing materials for electrical and electronic parts. Specific examples are given below.
• For surface protection it can be used for various materials such as metal, plastic, rubber, and wood. Specifically, it is used for surface protection of painted surfaces, plastic processing and deep drawing of metals, automobile parts, and optical parts. Available. Examples of the automobile parts include painted outer panels, wheels, mirrors, windows, lights, light covers, and the like. Examples of the optical member include various image display devices such as a liquid crystal display, an organic EL display, a plasma display, and a field emission display; ⁇ Precision fine-coated face plates for optical applications.
• Masking applications include masking during manufacturing of printed circuit boards and flexible printed circuit boards; masking during plating and soldering in electronic equipment; manufacturing of vehicles such as automobiles, painting and printing of vehicles and buildings, and masking during civil engineering work. etc.
• Packaging applications include heavy duty packaging, export packaging, cardboard box sealing, and can sealing.
• Office uses include general office use, sealing, repair of books, drafting, memo use, and the like.
• Label applications include price, product display, luggage tags, POP, stickers, stripes, nameplates, decorations, advertisements, marking films, and the like.
• Label applications include paper, processed paper (paper with aluminum vapor deposition, aluminum laminating, varnishing, resin processing, etc.), paper such as synthetic paper; cellophane, plastic materials, cloth, wood and metal
• a label having a film or the like as a base layer is exemplified.
• base material layers include woodfree paper, art paper, cast paper, thermal paper, wheel paper, polyethylene terephthalate film, polyvinyl chloride film, OPP film, polylactic acid film, synthetic paper, synthetic paper thermal, over-laminated film, and the like. are mentioned.
• Examples of the adherend of the above label include plastic products such as plastic bottles and foamed plastic cases; paper and cardboard products such as cardboard boxes; glass products such as glass bottles; metal products; be done.
• Decorative and display applications include danger display stickers, line tapes, wiring markings, phosphorescent tapes, and reflective sheets.
• Examples of adhesive optical film applications include polarizing films, polarizing plates, retardation films, viewing angle widening films, brightness enhancement films, antireflection films, anti-glare films, color filters, light guide plates, diffusion films, prism sheets, and electromagnetic wave shielding films. , near-infrared absorbing films, functional composite optical films, films for laminating ITO, films for imparting impact resistance, films for improving visibility, etc. mentioned. Such adhesive optical films also include protective films used for surface protection of the optical films. Adhesive optical films are suitably used for various image display devices such as liquid crystal display devices, PDPs, organic EL display devices, electronic papers, game machines, and mobile terminals.
• Electrical insulation applications include protective coating or insulation for coils, and interlayer insulation for motors and transformers.
• Applications for holding and fixing electronic devices include carrier tapes, packaging, fixing of cathode ray tubes, splicing, rib reinforcement, and the like. For semiconductor manufacturing, it can be used to protect silicone wafers.
• pain relief anti-inflammatory agents plaster, poultice
• patches for colds for colds
• antipruritic patches percutaneous absorption medicine applications
• percutaneous absorption medicine applications such as keratin softeners
• tape applications such as hemostats, tapes for human excrement treatment attachments (tape for fixing colostomy), suture tapes, antibacterial tapes, fixing tapings, self-adhesive bandages, oral mucosa adhesive tapes, sports tapes, hair removal tapes, etc.
• cosmetic applications such as face packs, moisturizing sheets around the eyes, exfoliating packs; binding applications for sanitary materials such as diapers and pet sheets;
• sealing materials for electronic and electrical parts include liquid crystal displays, organic EL displays, organic EL lighting, and solar cells.
• Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) The weight average molecular weight and number average molecular weight of the acrylic block copolymer were determined by gel permeation chromatography (hereinafter abbreviated as GPC) in terms of polystyrene equivalent molecular weight, and the molecular weight distribution was calculated from these values.
• GPC gel permeation chromatography
• composition ratio of each polymer block Obtained by 1 H-NMR measurement.
• Apparatus Nuclear magnetic resonance apparatus "JNM-LA400” manufactured by JEOL Ltd.
• Heavy solvent Deuterated chloroform
• signals near 3.6 ppm, 3.7 ppm and 4.0 ppm are carbon atoms adjacent to oxygen atoms contained in ester groups of methyl methacrylate units, respectively.
• the molar ratio of each monomer unit is obtained from the ratio, and the content of each polymer block is obtained by converting this into a mass ratio based on the
• solubility parameters SP(A1) and SP(B1) of polymer blocks (A1) and (B1) were obtained by the Fedors estimation method.
• the values of the methyl acrylate unit, the n-butyl acrylate unit, and the 2-ethylhexyl acrylate unit contained in each polymer block the values described above were used as they were.
• the details of the case where each polymer block is a polymer block composed of a plurality of monomer units will be described below with reference to embodiments.
• the solubility parameter of the homopolymer corresponding to the monomer units contained in the polymer block was used.
• the solubility parameters for the homopolymers included in the synthesis examples below are: polymethyl acrylate (methyl acrylate units), poly n-butyl acrylate (n-butyl acrylate units), poly 2-ethylhexyl acrylate (acrylic acid 2-ethylhexyl unit) and ⁇ E and V of polymethyl methacrylate (methyl methacrylate unit), which are 11.30 (cal/cm 3 ) 1/2 and 10.20 (cal/cm 3 ) 1/2 respectively. , 9.50 (cal/cm 3 ) 1/2 and 10.50 (cal/cm 3 ) 1/2 .
• the solubility parameter SP(C) of oleic acid is 9.14 (cal/cm 3 ) 1/2 .
• the index value of the solubility parameter of the acrylic block copolymer (I-1) used in Example 1 is 10.46 (cal/cm 3 ). Asked for 1/2 .
• Oleic acid immersion test A disc having a diameter of 25 mm was punched out from the press sheets prepared in Examples and Comparative Examples, and the disc was used as a test piece. First, the mass of the test piece was measured and defined as the mass before immersion (W 1 ). Next, the test piece was immersed in oleic acid at 25° C. for 168 hours, and then the test piece was taken out and oleic acid adhering to the surface was wiped off. The mass of this test piece was measured and defined as the mass (W 2 ) after the immersion test. Then, from the above W 1 and W 2 , the mass change rate (W 2 ⁇ W 1 )/W 1 in the immersion test was determined as a percentage.
• Examples 1 to 7 which satisfy the provisions of the present invention, had a small mass change rate in the oleic acid immersion test.
• the molded articles obtained in Examples 1 to 7 had low hardness and retained flexibility.
• Comparative Example 1 a composition obtained by adding 500 parts by mass of the acrylic block copolymer (II-4) to the acrylic block copolymer (I-1) and a molded article of the composition were investigated. However, although the resulting molded article retained its flexibility, the rate of mass change in the oleic acid immersion test was large, and the shape could not be maintained.
• Comparative Example 2 100 parts by mass of an acrylic block copolymer (II'-1) having a high polymer block (A2) content was added to the acrylic block copolymer (I-1). A product and a molded product of the composition were examined. However, although the resulting molded article had a good mass change rate in the oleic acid immersion test, it could not maintain its flexibility.

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• 2021
  • 2021-04-07 JP JP2021065181A patent/JP2021120452A/ja active Pending
• 2022
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