JP2020059790A - Resin composition and article formed from the resin composition - Google Patents

Abstract

To provide a modifier capable of improving the impact resistance in an article.SOLUTION: A modifier (A) of the present invention has a reactive group X, and a dangling chain at a terminal, and has energy absorption index of 1 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition and an article formed from the resin composition.

  Resins exhibit various physical and chemical properties depending on their structure and are used in various fields such as industrial products and daily necessities. A typical method for adjusting the properties of the resin is to control the structure of the molecular chain, but if the molecular chain is made rigid to improve the mechanical strength of the resin, the toughness and impact resistance will decrease. On the other hand, when the molecular chain is made flexible to improve the toughness and impact resistance, there is a problem that the mechanical strength is reduced.

  Modifiers have been used to address such problems. For example, Patent Document 1 describes a thermoplastic molding composition containing a thermoplastic material composed of an aliphatic amide and an amorphous partially aromatic polyamide, and an impact modifier and the like.

Japanese Patent Laid-Open No. 2015-120909

  However, the hitherto known compositions may not have sufficiently satisfactory impact absorption. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a modifier capable of improving impact resistance of a molded body.

The modifying agent (A) of the present invention has a reactive group X and a dangling chain at the end,
The energy absorption index measured by the following method is more than 1.
[Measurement method of energy absorption index]
(1) The amount of the dangling chain in the total of the modifier and the standard polymer having the same main chain skeleton as the modifier and the reactive group X. Is mixed so as to be 0.03 mol / kg or more and 0.08 mol / kg or less.
(2) The mixture and the curing agent having a group Y capable of reacting with the reactive group X have a mass ratio of the mixture and the curing agent (mass of mixture / mass of curing agent) represented by the following formula. It mixes so that it may become a value represented, and it hardens, and hardened | cured material C1 is obtained.
Mass of mixture / mass of curing agent = 1.05 × (group X equivalent of mixture / group Y equivalent of curing agent)
(3) The dynamic mechanical properties of the cured product C1 are measured according to JIS K 7244, and the minimum tan δ value in the rubber elastic region in the obtained tan δ spectrum is tan δ ₁ .
(4) Separately, 100 parts by mass of the standard polymer and the curing agent, and the mass ratio of the standard polymer and the curing agent (mass of standard polymer / mass of curing agent) are represented by the following formulas: To obtain a cured product C0.
Mass of standard polymer / mass of curing agent = 1.05 × (group X equivalent of standard polymer / group Y equivalent of curing agent)
(5) The dynamic mechanical properties of the cured product C0 are measured according to JIS K 7244, and in the obtained tan δ spectrum, the minimum tan δ value in the rubber elastic region is tan δ ₀ .
(6) Let tan δ ₁ / tan δ ₀ be the energy absorption index.

  By using the modifier of the present invention, it is possible to provide a molded article having excellent impact absorption.

FIG. 1 shows the tan δ spectra of Standard Example 1 and Example 1.

The modifier (A) of the present invention has a reactive group X and a dangling chain at the terminal, and the energy absorption index measured by the following method is more than 1.
[Measurement method of energy absorption index]
(1) The amount of the dangling chain in the total of the modifier and the standard polymer having the same main chain skeleton as the modifier and the reactive group X. Is mixed so as to be 0.03 mol / kg or more and 0.08 mol / kg or less.
(2) The mixture and the curing agent having a group Y capable of reacting with the reactive group X have a mass ratio of the mixture and the curing agent (mass of mixture / mass of curing agent) represented by the following formula. It mixes so that it may become a value represented, and it hardens, and hardened | cured material C1 is obtained.
Mass of mixture / mass of curing agent = 1.05 × (group X equivalent of mixture / group Y equivalent of curing agent)
(3) The dynamic mechanical properties of the cured product C1 are measured according to JIS K 7244, and the minimum tan δ value in the rubber elastic region in the obtained tan δ spectrum is tan δ ₁ .
(4) Separately, 100 parts by mass of the standard polymer and the curing agent, and the mass ratio of the standard polymer and the curing agent (mass of standard polymer / mass of curing agent) are represented by the following formulas: To obtain a cured product C0.
Mass of standard polymer / mass of curing agent = 1.05 × (group X equivalent of standard polymer / group Y equivalent of curing agent)
(5) The dynamic mechanical properties of the cured product C0 are measured according to JIS K 7244, and in the obtained tan δ spectrum, the minimum tan δ value in the rubber elastic region is tan δ ₀ .
(6) Let tan δ ₁ / tan δ ₀ be the energy absorption index.

  The modifying agent (A) of the present invention has a reactive group X and a dangling chain and has an energy absorption index within a specific range. By using the modifying agent (A) of the present invention, Even when an impact is applied, the dangling chains existing in the gaps between the molecular chains can sufficiently absorb the impact, and it is possible to provide a resin molded article having excellent impact absorbability. The dangling chain may be present at the end of the polymer main chain of the modifier (A) or may be present in the side chain bonded to the polymer main chain.

  The energy absorption index is preferably 1.5 or more, more preferably 2 or more, still more preferably 2.5 or more, still more preferably 3 or more, and the upper limit is not limited, but for example, 100 or less, further 20 or less, In particular, it can be 10 or less.

  Examples of the reactive group X include an isocyanate group, a hydroxyl group, an epoxy group, a carboxyl group and an amino group, and an isocyanate group is preferable.

  The dangling chain is preferably a group containing a polymer chain and a group having a rigid portion bonded to the end of the polymer chain. By having a structure in which a group having a rigid portion is bonded to the end of the polymer chain, the dangling chain existing in the gap between the molecular chains becomes easier to absorb the impact.

  The polymer chain can be selected according to the resin used in the resin molded body, and examples thereof include a polyester chain, a polyolefin chain, a polyamide chain, a poly (meth) acrylic chain, a poly (meth) acrylamide chain, a polycarbonate chain, It may be a polystyrene chain, a polyarylene sulfide chain, a polyarylene ether chain or the like, preferably a polyether chain, a polyester chain, a polycarbonate chain and a polymer chain in which these are combined, more preferably a polyether chain or a polyester chain. The polymer chain may have a side chain.

  As the polyether chain, a polyoxyalkylene chain having a repeating unit of an oxyalkylene group having 2 to 6 carbon atoms, such as a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, a polyoxyalkylbutylene chain; A repeating unit is a group in which a substituent such as an aromatic hydrocarbon group or a halogen atom is bonded to the oxyalkylene group having 2 to 6 carbon atoms such as oxychloromethylethylene chain, polyoxyalkylbutylene chain or polyoxystyrene chain. A substituted polyoxyalkylene chain and the like, and a polyoxyalkylene chain is preferable.

  The polyester chain represents a polymer chain having a repeating unit containing an ester bond (—CO—O—), and may be a polymer chain having a repeating unit represented by the formula (1) and / or the formula (2). preferable.

[In formulas (1) and (2),
R ¹ represents an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the aliphatic hydrocarbon -CH ₂ contained in the hydrogen radical - may be replaced by -O-.
R ² represents an aliphatic hydrocarbon group having 1 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. ]

Examples of the aliphatic hydrocarbon group represented by R ¹ or R ² or a group in which —CH ₂ — contained in the aliphatic hydrocarbon group is replaced with —O— include an ethylene group, a propylene group, and 1,4-butanediyl. Group, 1,5-pentanediyl group, 1,6-hexanediyl group, 2-methyl-1,3-propanediyl group, 3-methyl-1,5-pentanediyl group, neopentanediyl group, 1,3-butanediyl group Groups, 3-oxapentane-1,5-diyl group, 4-oxaheptane-2,6-diyl group, 4-oxaheptane-1,7-diyl group and other bifunctional groups; trimethylolpropane, glycerin, etc. And a trifunctional group such as an ether residue.

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ¹ and R ² is preferably 2 or more, preferably 10 or less, more preferably 8 or less.

Examples of the alicyclic hydrocarbon group represented by R ¹ include a 1,4-cyclohexanediyl group and a 1,4-dimethylcyclohexanediyl group. In the present invention, the alicyclic hydrocarbon group represents a group having an alicyclic structure, and includes both a group consisting of only an alicyclic structure and a group combining an alicyclic structure and an aliphatic hydrocarbon group. Let's assume.

The number of carbon atoms of the alicyclic hydrocarbon group represented by R ¹ is preferably 5 or more, more preferably 6 or more, preferably 10 or less, more preferably 8 or less.

The aromatic hydrocarbon group represented by R ¹ and R ² is an ether of a 2,2-diphenylpropanediyl group, a 1,1-diphenylmethanediyl group and a group in which an alkylene oxide is added to a bisphenol compound such as bisphenol A and bisphenol. Examples thereof include residues. In the present invention, a group containing an aromatic ring structure is represented, and both a group consisting of an aromatic ring structure and a group combining an aromatic ring structure and an aliphatic hydrocarbon group are included.

The aromatic hydrocarbon group represented by R ¹ and R ² preferably has 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 25 or less carbon atoms.

  The polyester chain represents a polymer chain having a repeating unit containing a carbonate bond (—O—CO—O—), and is preferably a polymer chain having a repeating unit represented by the formula (3).

[In the formula (3),
R ³ represents an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. ]

Examples of the aliphatic hydrocarbon group represented by R ³ include the same groups as those exemplified as the aliphatic hydrocarbon group represented by R ¹ . The number of carbon atoms of the aliphatic hydrocarbon group represented by R ³ is preferably 2 or more, preferably 10 or less, more preferably 8 or less.

Examples of the alicyclic hydrocarbon group represented by R ³ include the same groups as those exemplified as the alicyclic hydrocarbon group represented by R ¹ . The number of carbon atoms of the alicyclic hydrocarbon group represented by R ³ is preferably 5 or more, more preferably 6 or more, preferably 10 or less, more preferably 8 or less.

Examples of the aromatic group represented by R ³ include the same groups as those exemplified as the aromatic hydrocarbon group represented by R ¹ . The aromatic hydrocarbon group represented by R ³ has preferably 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 25 or less carbon atoms.

  The number average molecular weight of the polymer chain is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, preferably 5,000 or less, more preferably 3,000 or less, still more preferably 2,000 or less. Is.

  In the present invention, the number average molecular weight and the weight average molecular weight can be measured as a conversion value using polystyrene as a standard sample, using a gel permeation chromatography method.

  Examples of the group having a rigid portion include an aromatic hydrocarbon group having 6 to 20 carbon atoms; -CO-NH-, -NH-CO-O-, -NH-CO-S-, -NH-CO-. Examples thereof include a group containing at least one kind of aggregating group such as NH-, may contain a short-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, and have an organosilyl group on the free end side. May be.

  The group having a rigid part is preferably a group represented by the formula (4).

［式（４）中、
Ａｒ¹は、芳香族炭化水素基を表す。
Ｒ⁴は、単結合、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基又はこれらの２種以上を組み合わせた基を表す。
Ｌ¹は、ウレタン結合基、ウレア結合基及びチオウレタン結合基からなる群より選ばれる１種を表し、前記ウレタン結合基、ウレア結合基及びチオウレタン結合基に含まれる水素原子は、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基又はこれらの２種以上を組み合わせた基に置換されていてもよく、さらに、該脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基又はこれらの２種以上を組み合わせた基に含まれる水素原子は、オルガノシリル基に置換されていてもよい。
Ｒ⁵は、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基又はこれらの２種以上を組み合わせた基を表し、該脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基に含まれる１又は２以上の水素原子は、オルガノシリル基に置換されていてもよい。］

[In formula (4),
Ar ¹ represents an aromatic hydrocarbon group.
R ⁴ represents a single bond, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group in which two or more kinds of these are combined.
L ¹ represents one kind selected from the group consisting of a urethane bond group, a urea bond group and a thiourethane bond group, and the hydrogen atom contained in the urethane bond group, the urea bond group and the thiourethane bond group is an aliphatic carbon atom. It may be substituted with a hydrogen group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group in which two or more of these are combined, and further, the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic The hydrogen atom contained in the group hydrocarbon group or the group formed by combining two or more of these groups may be substituted with an organosilyl group.
R ⁵ represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group in which two or more kinds of these are combined, and the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic group One or more hydrogen atoms contained in the group hydrocarbon group may be substituted with an organosilyl group. ]

Examples of the aliphatic hydrocarbon group represented by R ⁴ include alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group and decandiyl group. preferable. The number of carbon atoms of the aliphatic hydrocarbon group represented by R ⁴ is preferably 1-10, more preferably 1-8, and further preferably 1-6.

Examples of the alicyclic hydrocarbon group represented by R ⁴ include a cyclohexanediyl group, a trimethylcyclohexanediyl group and a tetramethylcyclohexanediyl group. The number of carbon atoms of the alicyclic hydrocarbon group represented by R ⁴ is preferably 3 to 12, more preferably 6 to 10.

Examples of the aromatic hydrocarbon group represented by Ar ¹ and R ⁴ include a phenylene group, a tolylene group, a xylylene group and a naphthylene group. The aromatic hydrocarbon group represented by Ar ¹ and R ⁴ preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

Examples of the group in which two or more kinds of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group represented by R ⁴ are combined include a dicyclohexylmethanediyl group, a diphenylmethanediyl group, a xylenediyl group, and tetramethyl. Examples thereof include xylenediyl group. The number of carbon atoms of the combined group is preferably 4 to 30, more preferably 10 to 20.

Examples of the aliphatic hydrocarbon group represented by R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group. , Isopentyl group, neopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, hexyl group, heptyl group, n-octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group, etc. A branched or branched alkyl group may be mentioned. The number of carbon atoms of the aliphatic hydrocarbon group represented by R ⁵ is preferably 1-10, more preferably 1-8, and even more preferably 1-6.

Examples of the alicyclic hydrocarbon group represented by R ⁵ include a cyclohexyl group, a trimethylcyclohexyl group and a tetramethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group represented by R ⁵ is preferably 3 to 12, more preferably 6 to 10.

Examples of the aromatic hydrocarbon group represented by R ⁵ include a phenyl group, a toluyl group, a xylyl group and a naphthyl group. The aromatic hydrocarbon group represented by R ⁵ preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

Examples of groups in which two or more kinds of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups represented by R ⁵ are combined include cyclohexylmethylcyclohexyl group, phenylmethylphenyl group, methylcyclohexylmethyl group, and the like. Is mentioned. The number of carbon atoms of the combined group is preferably 4 to 30, more preferably 10 to 20.

The organosilyl group represents a group composed of a silicon atom and three organic groups bonded to the silicon atom, and may be a reactive organosilyl group or a non-reactive organosilyl group, It is preferably a group represented by formula (5). When the group represented by R ⁵ is substituted with an organosilyl group, the organosilyl group is gently aggregated in the molded body, and it becomes easier to further improve the impact absorbability.

[In the formula (5), R ^6's each independently represent one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, an acetoxy group and a halogen atom group.
R ⁷ represents a hydrocarbon group having 1 to 5 carbon atoms.
a represents the integer of 0-3.
* Represents a bond. ]

Examples of the alkoxy group represented by R ⁶ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group. The alkoxy group may be linear or branched, and the number of carbon atoms of the alkoxy group is preferably 1 to 4.

R ⁶ is preferably a hydroxyl group or an alkoxy group.

The hydrocarbon group represented by R ⁷ is preferably an aliphatic hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group; an ethenyl group, a propenyl group, butenyl. Group, an alkenyl group such as a pentenyl group; an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a pentynyl group and the like, and an alkyl group is preferable. The hydrocarbon group may be linear or branched, and the number of carbon atoms of the hydrocarbon group is preferably 1 to 4, more preferably 1 to 3.

R ⁴ is preferably a single bond or a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined.

As R ⁵ , an aliphatic hydrocarbon group is preferable.

As L ¹ , a urethane bond group or a urea bond group is preferable.

  The amount of dangling chains contained in the modifier (A) is preferably 0.01 mol / kg or more, more preferably 0.05 mol / kg or more, even more preferably 0.1 mol / kg or more, even more preferably. Is 0.2 mol / kg or more, preferably 10 mol / kg or less, more preferably 5 mol / kg or less, even more preferably 2 mol / kg or less, even more preferably 1.5 mol / kg or less.

  The polymer main chain of the modifier (A) can be appropriately selected, for example, according to the resin constituting the resin molded body, and a polyester chain, a polyolefin chain, a polyamide chain, a poly (meth) acrylic chain, a poly ( It may be a (meth) acrylamide chain, a polycarbonate chain, a polystyrene chain, a polyarylene sulfide chain, a polyarylene ether chain, a urethane chain, or the like, preferably a urethane chain.

  The modifying agent (A) preferably has an isocyanate group as the reactive group X. The group X equivalent of the modifier (A) is preferably 200 or more, more preferably 300 or more, preferably 3000 or less, more preferably 2000 or less.

  When the modifier (A) contains an isocyanate group, the isocyanate group does not have to react with the resin to be modified, but reacts with the resin to be modified to form a urethane bond or a urea bond. Preferably.

  The modifier (A) contains a compound capable of forming a polymer main chain, a compound having a group capable of forming an aggregating group such as a hydroxyl group, a thiol group, an amino group and an isocyanate group, and an active hydrogen atom. A reaction product of the compound (x3) and / or the compound (x4) having an organosilyl group is preferable, and the polyol (x1), the polyisocyanate (x2), and the compound (x3) containing an active hydrogen atom and / or Alternatively, it is preferably a reaction product with a compound (x4) having an organosilyl group. The compound capable of forming the main chain and the compound having a group capable of forming an aggregating group may be the same or different.

  Examples of the polyol (x1) include polymer polyols such as polyether polyols, polyester polyols, polycarbonate polyols and polylactone polyols; and low molecular weight polyols.

  As the polyether polyol, a polyoxyalkylene polyol is preferable, and if necessary, one or more compounds having two or more active hydrogen atoms are used as an initiator, and a cyclic ether such as an alkylene oxide is subjected to ring-opening polymerization. Some of them have been made.

  The number of carbon atoms of the cyclic ether is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. The hydrogen atom contained in the cyclic ether may be substituted with a halogen atom. As said cyclic ether, 1 type (s) or 2 or more types can be used, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, alkyl. And tetrahydrofuran.

  As said initiator, 1 type (s) or 2 or more types can be used, for example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-. Hexanediol, neopentyl glycol, compounds having two active hydrogen atoms such as water; glycerin, diglycerin, trimethylolethane, trimethylolpropane, hexanetriol, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, pentaerythritol, Examples thereof include compounds having 3 or more active hydrogen atoms such as saccharides.

  Examples of the polyester polyols include polyester polyols obtained by esterifying a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 300 or less) and a polycarboxylic acid; a ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. Polyester polyols obtained by reaction; copolymerized polyester polyols thereof and the like can be mentioned.

  As the low molecular weight polyol used for producing the polyester polyol, a polyol having a molecular weight of 50 or more and 300 or less can be used, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, trimethylol Aliphatic polyols having 2 to 6 carbon atoms such as propane and glycerin (diols or trifunctional polyols); alicyclic structure-containing polyols such as 1,4-cyclohexanediol and cyclohexanedimethanol; bisphenol A, bispheno And aromatic structure-containing polyol of bisphenol compounds and their alkylene oxide adducts such as F and the like.

  Examples of the polycarboxylic acid used in the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic compounds such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid. Polycarboxylic acids; and anhydrides or ester-forming derivatives of the above aliphatic polycarboxylic acids and aromatic polycarboxylic acids.

  Examples of the polycarbonate polyol include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.

  Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

  Examples of the polyol capable of reacting with the carbonic acid ester include polyols exemplified as the low molecular weight polyols; high molecular weight polyols (weight, such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.). The average molecular weight is 500 or more and 5,000 or less).

  As the polylactone polyol, one or more selected from the group consisting of the polyether polyol, polyester polyol, and polycarbonate polyol and / or a low molecular weight polyol used in the production of the polyester polyol is used as an initiator to react with a lactone compound ( Those added) can be used.

  As the lactone compound, one kind or two or more kinds can be used, and for example, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl- ε-caprolactone, γ-methyl-ε-caprolactone, β, δ-dimethyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, enanthlactone (7-heptanolide), dodecanolactone (12-dodecanolide) Etc. can be used.

  The addition rate of the lactone compound is preferably 5% by mass or more with respect to 100 parts by mass of the total of one or more kinds selected from the group consisting of the polyether polyol, polyester polyol and polycarbonate polyol and / or the low molecular weight polyol, It is more preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.

  The functional number of the polymer polyol is 2 or more, may be 3 or more, and is preferably 5 or less.

  The number average molecular weight of the polymer polyol is preferably 300 or more, more preferably 500 or more, preferably 5,000 or less, more preferably 3,000 or less.

  The content ratio of the polymer polyol in the polyol (x1) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and the upper limit is 100% by mass.

  As the low molecular weight polyol as the polyol (x1), one kind or two or more kinds can be used, and examples thereof include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol and 2-methyl-. 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (2,2-dimethyl-1,3- Propanediol), 2-isopropyl-1,4-butanediol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol , 2-methyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-die Ru-1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 1,7-heptane Aliphatic diols such as diol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol; glycerin, trimethylol Aliphatic triols such as propane; cyclohexanedimethanol (eg 1,4-cyclohexanedimethanol), cyclohexanediol (eg 1,3-cyclohexanediol, 1,4-cyclohexanediol), 2-bis (4-hydroxycyclohexyl)- Examples thereof include alicyclic diols such as propane.

  When the low molecular weight polyol is contained, the content of the low molecular weight polyol is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the polymer polyol.

  As said polyisocyanate (x2), 1 type (s) or 2 or more types can be used, for example, cycloisocyanate diisocyanate, dicyclohexylmethane diisocyanate, the polyisocyanate which has alicyclic structure, such as isophorone diisocyanate; 4,4'- diphenylmethane diisocyanate. Aromatic polyisocyanates such as 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate Aliphatic polyisocyanates such as And the like.

  As the compound (x3) containing an active hydrogen atom, one kind or two or more kinds can be used, and for example, an alcohol compound, an amine compound and the like can be used. As said alcohol compound, 1 type (s) or 2 or more types can be used, for example, monoalcohol, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol. Compounds: Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc. Monoalkyl ether; polyoxyethylene lauryl , Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether and other polyoxyethylene alkyl ethers; polyoxyethylene oleyl ether and other polyoxyethylene alkenyl ethers; polyoxyethylene Polyoxyalkylene alkyl ether such as polyoxypropylene alkyl ether; polyethylene glycol monoalkylate (polyethylene glycol monolaurate, polyethylene glycol monostearate, etc.), polyethylene glycol monoalkenylate (polyethylene glycol monooleate, etc.), polyethylene glycol Polyalkyl such as dial chelate (polyethylene glycol distearate) Polyethylene ethylene hydrogenated castor oil; Polyoxyethylene alkylamines; Alkyl alkanolamides; Polyoxyethylene distyrenated phenyl ethers; Polyoxyethylene tribenzyl phenyl ethers; Polyoxyethylene glycols, Polyoxypropylene glycols , Polyoxyalkylene glycols such as polyoxyethylene polyoxypropylene glycol; sorbitan fatty acid monoesters (sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, etc. ), Sorbitan fatty acid diester (sorbitan distearate, etc.), sorbitan fatty acid triester (sorbitan Sorbitan fatty acid esters such as tristearate, sorbitan trioleate, etc .; alkyl alkanolamides such as palm kernel oil fatty acid diethanolamide, lauric acid diethanolamide, coconut fatty acid N-methylethanolamide; alkyl polyglycoside such as decyl glucoside, lauryl glucoside And so on.

  Examples of the amine compound include primary monoamine compounds such as propylamine, butylamine and octylamine; secondary monoamine compounds such as dimethylamine, dipropylamine, diethylamine, dibutylamine, dioctylamine and diisopropylamine; N, N- Tertiary monoamine compounds such as cyclohexylmethylamine, N, N-dimethylcyclohexylamine; 3-dimethylaminopropylurea, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminoethylmorpholine, N, N, N '. N '. N "-pentamethyldiethylene triamine, bis (3-dimethylaminopropyl) -N, N-dimethylpropanediamine, N, N, N7-trimethyl-2-hydroxyethylpropylenediamine, N, N ', N" -dimethyl Aminopropylhexahydrotriazine, bis (dimethylaminopropyl) methylamine; quaternary ammonium salt; 1,4-diazabicyclo [2.2.2] octane, 1,4-diazabicyclo [2.2.2] octane compound Salt, salt of 1,4-diazabicyclo [2.2.2] octane, 2-methyltriethylenediamine, mixture of 1,4-diazabicyclo [2.2.2] octane and dimethylethanolamine, 1,4-diazabicyclo A heterocyclic amine such as a mixture of [2.2.2] octane and 1,4-butanediol, or Salts thereof, and the like.

  The compound (x3) containing an active hydrogen atom can enhance the impact absorbability even if it is not a bulky compound such as a monoalcohol compound.

  The amount of the compound (x3) containing an active hydrogen atom is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more with respect to 100 parts by mass of the polyol (x1). It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

  Examples of the organosilyl group-containing compound (x4) include compounds having the organosilyl group and a group having an active hydrogen atom such as a hydroxyl group, an amino group and a mercapto group, an epoxy group or an isocyanate group.

  As the compound having an organosilyl group and a hydroxyl group, one kind or two or more kinds can be used, and for example, hydroxymethyltrimethoxysilane, 1,4-bis (hydroxydimethylsilyl) benzene, 1,3- Bis (3-hydroxypropyl) -1,1,3,3-tetramethyldisiloxane, heptamethyl-3- (3-hydroxypropyltrisiloxane), 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, etc. And a reactive or non-reactive organosilyl group-containing compound having one or more hydroxyl groups.

  As the compound having an organosilyl group and an amino group, one kind or two or more kinds can be used, and examples thereof include dimethylaminotrimethylsilane, bis (dimethylaminomethylsilane), allylaminotrimethylsilane, and 3-aminopropyl. Trimethoxysilane, bis (dimethylamino) dimethylsilane, 2-aminoethylaminomethyltrimethylsilane, tris (dimethylamino) silane, bis (dimethylamino) methylvinylsilane, diethylaminotrimethylsilane, 3-aminopropyldimethylethoxysilane, methyltris ( Dimethylamino) silane, allyloxy-2-aminoethylaminomethyldimethylsilane, 3-aminopropyldiethylaminomethyldimethylsilane, 3-aminopropyldiethoxymethylsilane, 3- ( -Aminoethylaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminophenoxydimethylvinylsilane, 4- Aminophenoxydimethylvinylsilane, 3-piperazinopropyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3- [2- (2-aminoethylamino) Ethylamino) propyl] trimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-cyclohexyl Aminopropyltrimethoxysilane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminoethylaminomethyl) -1,1,3,3-tetramethyldisiloxane, 1 , 4-bis (3-aminopropyldimethylsilyl) benzene, 3- (2-aminoethylaminopropyl) tris (trimethoxysiloxy) silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N -2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-trimethoxysilyl-N- ( 1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopyropyrtrimethoxysilane Reactive or non-reactive organosilyl having one or more amino groups such as silane, bis (3-trimethoxysilylpropyl) amine, N- (n-butyl) -3-aminopropyltrimethoxysilane Examples thereof include group-containing compounds or salts thereof.

  As the compound having an organosilyl group and a mercapto group, one kind or two or more kinds can be used, and for example, mercaptomethyltrimethoxysilane, mercaptomethyltrimethylsilane, dimethoxy-3-mercaptopropylmethylsilane, 3- Examples thereof include reactive or non-reactive organosilyl group-containing compounds having one or more mercapto groups such as mercaptopropyltrimethoxysilane and 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane. .

  As the compound having an organosilyl group and an epoxy group, one type or two or more types can be used, and examples thereof include 3-glycyloxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexylethyl) trimethoxy. Silane, diethoxy-3-glycidoxypropylmethylsilane, 3-glycidoxypropyltriethoxysilane, 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane, etc. Examples thereof include a reactive or non-reactive organosilyl group-containing compound having one or more epoxy groups.

  Examples of the compound having an organosilyl group and an isocyanate group include 3-isocyanatopropyltriethoxysilane.

  The amount of the organosilyl group-containing compound (x4) is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 2 parts by weight, based on 100 parts by mass of the polyol (x1). It is above, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and further preferably 30 parts by weight or less.

  An isocyanate group contained in the polyisocyanate (x2), a group having an active hydrogen atom contained in the polyol (x1), the compound (x3) containing the active hydrogen atom, and the organosilyl group-containing compound (x4) (hydroxyl. Group, amino group, mercapto group, etc.), the equivalent ratio (NCO / H) is preferably 1.3 or more, more preferably 1.5 or more, preferably 6.5 or less, more preferably 4 or less, It is particularly preferably 3 or less.

  The modifier (A) is a reaction product of the polyol (x1), the polyisocyanate (x2), the compound (x3) containing the active hydrogen atom and / or the organosilyl group-containing compound (x4), and It may be a reaction product with a chain extender (x5) (that is, it may be a urethane elastomer cured product). As the chain extender (x5), a compound having a group containing an active hydrogen atom ([NH] group and / or [OH] group) can be used, and specifically, a polyamine compound, a hydrazine compound, The compounds similar to the compounds exemplified as the low molecular weight polyol as the polyol (x1) can be mentioned.

  Of the compounds exemplified as the low molecular weight polyol as the polyol (x1), an aliphatic polyol (aliphatic diol, aliphatic triol, etc.) is preferable.

  Examples of the polyamine compound include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,3 ′. -Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like can be mentioned.

  Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide Propionic acid hydrazide and the like can be mentioned.

  Included in the chain extender (x5) and an isocyanate group contained in the reaction product of the polyol (x1), polyisocyanate (x2), compound (x3) containing an active hydrogen atom, and organosilyl group-containing compound (x4). When the molar ratio ([NCO / H]) to the active hydrogen atom is around 1.0 (for example, 0.9 to 1.1), the reaction product of the reaction product and the chain extender (x5) is , Tend to be high molecular weight and harden.

  The number average molecular weight of the modifier (A) is preferably 250 or more, more preferably 500 or more, preferably 10,000 or less, more preferably 5000 or less.

In the present invention, the weight average molecular weight and the number average molecular weight represent the values measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.
The standard polymer used for measuring the energy absorption index may have the same main chain skeleton as the modifier and the reactive group X, and may be a polyester resin, a polyolefin resin, a polyamide resin, a polyresin. Examples thereof include (meth) acrylic resin, poly (meth) acrylamide resin, polycarbonate resin, polystyrene resin, polyarylene sulfide resin, polyarylene ether resin, and urethane resin, and urethane resin is more preferable.

  The standard polymer is preferably a reaction product of a compound capable of forming a polymer main chain of the modifier, and the polyol (x1), polyisocyanate (x2) and a chain extender (x5) used as necessary. It is preferable that it is a reaction product (that is, it may be a urethane elastomer cured product).

  The equivalent ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate (x2) and the hydroxyl group contained in the polyol (x1) is preferably 1.3 or more, more preferably 1.5 or more. , Preferably 6.5 or less, more preferably 4 or less, particularly preferably 3 or less.

  The isocyanate group equivalent of the standard polymer is preferably 200 or more, more preferably 300 or more, preferably 3000 or less, more preferably 2000 or less.

  In addition, in this specification, a functional group equivalent shall represent the molecular weight per 1 functional group child.

  The amount of dangling chains contained in the total of the modifier (A) and the standard polymer is 0.03 mol / kg or more and 0.08 mol / kg or less, preferably 0.05 mol / kg or more, and more preferably , 0.06 mol / kg or more.

  The modifying aid (A1) can be produced by reacting the polyol (x1), the polyisocyanate (x2) and the chain extender (x5) used as necessary. When the modifying aid (A1) is used in combination, the modifying agent (A) and the modifying aid (A1) may be separately produced and then mixed to produce the modifying agent (A). Reacting the polyol (x1), the polyisocyanate (x2), the compound (x3) containing an active hydrogen atom and / or the organosilyl group-containing compound (x4), and a chain extender (x5) optionally used. Then, a mixture of the modifier (A) and the modifier aid (A1) may be directly produced. In any case, the amount of dangling chains contained in the total of the modifier (A) and the modifier aid (A1) is preferably within the above range.

  The curing agent used for measuring the energy absorption index may be one having a group Y capable of reacting with the reactive group X, and examples of the group Y include a hydroxyl group, an isocyanate group, a carboxyl group, Examples thereof include an epoxy group and an amino group. Of these, a hydroxyl group is preferable. As the curing agent, for example, the compounds exemplified as the chain extender (x5) can be used, and the compounds exemplified as the low molecular weight polyol as the polyol (x1) are preferable. As the curing agent, one kind or two or more kinds of compounds can be used.

  The group Y equivalent of the curing agent is preferably 30 or more, more preferably 40 or more, preferably 150 or less, more preferably 100 or less, still more preferably 60 or less.

  The average molecular weight of the curing agent is preferably 60 or more, more preferably 80 or more, preferably 300 or less, more preferably 200 or less, still more preferably 120 or less. The average molecular weight of the curing agent can be determined based on the chemical formula weight, and when two or more compounds are contained, it can be calculated as a weight-based weighted average value.

  A resin composition containing the modifier (A) and the organic polymer (B) is also included in the technical scope of the present invention.

  The content of the modifier (A) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, preferably 90% by mass. The amount is preferably 70% by mass or less, more preferably 70% by mass or less, and further preferably 50% by mass or less.

  The organic polymer (B) may be a thermoplastic resin or a thermosetting resin, or may be a mixture containing two or more kinds of organic polymers. Examples of the thermoplastic resin include urethane resin (urethane prepolymer), polyester resin, polyolefin resin, polyamide resin, (meth) acrylate resin, (meth) acrylamide resin, polycarbonate resin, polystyrene resin, polyarylene sulfide resin, polyarylene ether. Resin etc. are mentioned. Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, melamine resin, urea resin, phenol resin, vinyl ester resin and the like.

  The organic polymer (B) preferably contains the organic polymer (b1) containing an active hydrogen atom. Examples of organic polymers containing active hydrogen atoms include polyamide resins, (meth) acrylamide resins, epoxy resins, benzoguanamine resins, melamine resins, urea resins, and phenol resins.

  The content of the organic polymer (b1) in the organic polymer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 100% by mass. % Or less.

  The resin composition contains, in addition to the modifier (A) and the organic polymer (B), a modification aid, another modifier, a catalyst, a curing agent, a filler, a pigment, a thickener, and an antioxidant. One or more kinds of agents, ultraviolet absorbers, surfactants, flame retardants, plasticizers, reinforcing fibers (glass (long fibers / short fibers), carbon fibers, etc.) and the like may be contained as additives.

  Examples of the modifying aid (A1) include polyester resin, polyolefin resin, polyamide resin, poly (meth) acrylic resin, poly (meth) acrylamide resin, polycarbonate resin, polystyrene resin, polyarylene sulfide resin, polyarylene ether resin, Examples of the urethane resin include polymers having the same main chain as the polymer main chain of the modifier (A), and urethane resins are more preferable.

  The modification aid (A1) is preferably a reaction product of a compound capable of forming a polymer main chain, and the polyol (x1), polyisocyanate (x2) and a chain extender (x5) used as necessary. It is preferable that it is a reaction product (that is, it may be a urethane elastomer cured product). As the modifying aid (A1), one kind or two or more kinds can be used.

  The equivalent ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate (x2) and the hydroxyl group contained in the polyol (x1) is preferably 1.3 or more, more preferably 1.5 or more. , Preferably 6.5 or less, more preferably 4 or less, particularly preferably 3 or less.

  The isocyanate group equivalent of the modifying aid (A1) is preferably 200 or more, more preferably 300 or more, preferably 3000 or less, more preferably 2000 or less.

  The content of the modifying aid (A1) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass with respect to 1 part by mass of the modifying agent (A). It is above, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 30 parts by mass or less.

  The amount of dangling chains contained in the total of the modifier (A) and the modifier aid (A1) is preferably 0.001 mol / kg or more, more preferably 0.005 mol / kg or more, and further preferably , 0.01 mol / kg or more, preferably 10 mol / kg or less, more preferably 5 mol / kg or less, still more preferably 0.5 mol / kg or less, even more preferably 0.2 mol / kg or less, particularly preferably 1 mol. / Kg or less.

  The modifying aid (A1) can be produced by reacting the polyol (x1), the polyisocyanate (x2) and the chain extender (x5) used as necessary. When the modifying aid (A1) is used in combination, the modifying agent (A) and the modifying aid (A1) may be separately produced and then mixed to produce the modifying agent (A). Reacting the polyol (x1), the polyisocyanate (x2), the compound (x3) containing an active hydrogen atom and / or the organosilyl group-containing compound (x4), and a chain extender (x5) optionally used. Then, a mixture of the modifier (A) and the modifier aid (A1) may be directly produced. In any case, the amount of dangling chains contained in the total of the modifier (A) and the modifier aid (A1) is preferably within the above range.

  The curing agent may be the same as or different from the curing agent used for measuring the energy absorption index, and for example, the compounds exemplified as the chain extender (x5) can be used. When it contains the curing agent, the organic polymer (B) may not contain the organic polymer (b1) containing an active hydrogen atom.

  Articles formed from the resin composition are also included in the scope of the present invention. In the article of the present invention, for example, the modifier (A), the organic polymer (B) and a curing agent used as necessary are mixed, heated, and molded as necessary (eg, extrusion molding, injection molding). It can be manufactured by molding. When the organic polymer (B) contains a urethane resin (urethane prepolymer), the organic polymer containing the urethane resin (urethane prepolymer), the modifier (A) of the present invention and a curing agent are mixed. By heat curing, the article of the present invention, which is a urethane elastomer, can be produced. When the organic polymer (B) contains an organic polymer (b1) containing an active hydrogen atom, an organic polymer (B) containing the modifier (A) and the organic polymer (b1). The articles of the present invention can be manufactured by mixing and molding (preferably extrusion molding).

  When forming the said article from the said resin composition, you may provide an aging process as needed. In the aging step, particularly when the modifying agent contains an organosilyl group, the hydrolysis / condensation reaction of at least a part of the organosilyl group proceeds, so that after aging, the mechanical properties (strength and the like of the resulting article) are increased. ) Tends to be stable. The aging temperature is, for example, 0 ° C. to 100 ° C., preferably 20 ° C. to 80 ° C., and the aging time is, for example, 100 hours to 10,000 hours, preferably 200 hours to 5,000 hours, and humidity during aging. Are, for example, 30% RH to 100% RH and 50% RH to 99% RH. The higher the temperature and / or the humidity, the shorter the aging time can be. Therefore, for example, the aging time can be shortened to 50 hours or less under the conditions of the aging temperature of 65 ° C. or more and the humidity of 95% RH or more. When the aging temperature is 25 ° C. to 35 ° C. and the humidity is 30% RH to 80% RH, the aging time is about 500 hours to 1000 hours.

  The article of the present invention is excellent in shock absorption and toughness, and can be used for sports goods, leisure goods, ship members, automobile members, aircraft members, building materials, electronic device members and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis examples (a1-1) to (a1-7)]
A 3 liter 4-neck round bottom flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer, and a stirrer was charged with methyl ethyl ketone and polyisocyanate (x2) in the composition shown in Table 1 as needed, and stirring was started. . Next, the polyol (x1) shown in Table 1 was charged and mixed, and the reaction was carried out at 70 ° C. for 3 hours in a nitrogen atmosphere. Then, the compound (x3) containing an active hydrogen atom shown in Table 1 was reacted at 70 ° C. for 5 hours while paying attention to heat generation. The groups represented by the formula (1) and isocyanate group-terminated urethane prepolymers (a1-1) to (a1-7) shown in Table 1 were obtained.

  In Table 1, the polyol (x1-1) represents a bifunctional polycaprolactone polyol (number average molecular weight 1,000), the polyol (x1-2) represents a trifunctional polycaprolactone polyol (number average molecular weight 850), The polyisocyanate (x2-1) represents 4,4′-diphenylmethane diisocyanate (MDI), the compound (x3-1) represents isopropyl alcohol, and the compound (x4-1) is N-phenyl-3-amino. Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-573”), and compound (x4-2) represents bis (3-trimethoxysilylpropyl) amine (“Dynasilan 1124” manufactured by Evonik). The compound (x3) (x4) concentration represents the total concentration of the compound (x3) and the compound (x4) in the raw material.

[Synthesis examples (a2-1) to (a2-2)]
A 5 liter 4-neck round bottom flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer, and a stirrer was charged with the polyisocyanate (x2) shown in Table 2 and stirring was started. Next, the polyol (x1) shown in Table 1 was charged and mixed, and the reaction was carried out at 70 ° C. for 3 hours in a nitrogen atmosphere. The isocyanate group-terminated urethane prepolymers ((a2-1) to (a2-2)) having the NCO equivalent shown in Table 2 were obtained.

  The polyol (x1-3) represents a bifunctional polycaprolactone polyol (number average molecular weight 1,000).

[Synthesis Examples (A-1) to (A-13)]
A urethane prepolymer shown in Table 3 was charged into a 3 liter 4-neck round bottom flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer, and a stirrer, and stirring was started. When (a1-1), (a1-3), (a1-5), or (a1-7) was used, depressurization (-0.1 MPa or less) treatment was performed at 80 ° C for 3 hours to remove the solvent ( De-MEK). After thorough mixing, the NCO equivalent was measured, and MDI was added in an amount calculated so as to have the NCO equivalent shown in Table 3. Urethane prepolymers (A-1) to (A-13) shown in Table 3 were obtained. The NCO equivalent was measured according to JIS K 7312.

[Examples 1-11, standard examples 1-2, comparative examples 1-2]
The mold release agent is applied to the drum of the centrifugal molding machine (drum diameter: 300 mm, depth: 200 mm), the drum temperature is 140 ° C., the drum rotation speed is 850 rpm, and the centrifugal molding machine is kept in standby.

As the main agent (i), the urethane prepolymers obtained in Synthesis Examples (A-1) to (A-13) and Synthesis Examples (a2-1) to (a2-2) were heated to 80 ° C. and a curing agent (ii). As a mixture, a mixture of 1,4-butanediol / trimethylolpropane in a weight ratio of 7/3 was adjusted to 40 ° C.
Next, the main component (i) in the number shown in Table 4 was charged into a disposable reaction container, the temperature was adjusted to 80 ° C., and then the curing agent (ii) at 40 ° C. was added in the number shown in Table 4 immediately. Stir with a high speed mixer for 40 seconds. Then, the main agent (i) / curing agent (ii) was subjected to vacuum defoaming treatment for 40 seconds and then put into a centrifugal molding machine. After 1 hour, the rotating drum was stopped and the urethane elastomer sheet adhered to the drum was taken out. The taken out sheet was subjected to after-curing at 110 ° C. for 16 hours. The sheet thickness was 2 mm. After that, the obtained sheet was left indoors for about 1 month, and then the tensile strength, the elongation, the tear strength, and the impact resilience were measured. For energy absorption performance, dynamic viscoelasticity was measured with a measurement frequency of 1 Hz. The results are shown in Tables 5-8.

The tensile strength, the elongation, and the tear strength were measured according to JIS K 7312 using a sheet having a thickness of 2 mm. Further, the compression set is a cylindrical test piece having a thickness of 12.5 mm and a diameter of 29.0 mm (i / ii liquid temperature = 80/40 ° C. cure temperature: 140 ° C. secondary cure: 110, separately from the 2 mm sheet formed by centrifugal molding. (° C. × 16 hours) was prepared and measured according to JIS K 7312.
Furthermore, the dynamic viscoelasticity (DMA) was measured as follows.
Using a sheet having a thickness of 2 mm, the dynamic viscoelasticity was measured according to JIS K 7244 according to the following procedure.
The storage elastic modulus (E ′) and loss elastic modulus (E ″) of the sheet were measured using a viscoelastic spectrometer (model: DMS6100, manufactured by SII Nanotechnology Inc.) in a temperature range of −100 to 250 ° C. The measurement was performed in the tension mode under the conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz, where tan δ = E ″ / E ′
Measurement condition:
(Sample size) 5 x 60 x 2 mm
(Span) 20mm
(Strain amount) 0.05%

The energy absorption index was measured by the following method.
[Measurement method of energy absorption index]
(1) The amount of the dangling chain in the total of the modifier and the standard polymer having the same main chain skeleton as the modifier and the reactive group X. Is mixed so as to be 0.03 mol / kg or more and 0.08 mol / kg or less.
(2) The mixture and the curing agent having a group Y capable of reacting with the reactive group X have a mass ratio of the mixture and the curing agent (mass of mixture / mass of curing agent) represented by the following formula. It mixes so that it may become a value represented, and it hardens, and hardened | cured material C1 is obtained.
Mass of mixture / mass of curing agent = 1.05 × (group X equivalent of mixture / group Y equivalent of curing agent)
(3) The dynamic mechanical properties of the cured product C1 are measured according to JIS K 7244, and the obtained tan δ spectrum has a minimum tan δ value in the rubber elastic region as tan δ ₁ .
(4) Separately, 100 parts by mass of the standard polymer and the curing agent, the mass ratio of the standard polymer and the curing agent (mass of standard polymer / mass of curing agent) is a value represented by the following formula: To obtain a cured product C0.
Mass of standard polymer / mass of curing agent = 1.05 × (group X equivalent of standard polymer / group Y equivalent of curing agent)
(5) The dynamic mechanical properties of the cured product C0 are measured according to JIS K 7244, and the minimum tan δ value in the rubber elastic region in the obtained tan δ spectrum is tan δ ₀ .
(6) Let tan δ ₁ / tan δ ₀ be the energy absorption index.

  The evaluation criteria are as follows.

<Temperature range>
The tan δ in the rubber elasticity region (region above the Tg peak temperature) was evaluated by the DMA measurement result. The temperature range in which the tan δ of the example or comparative example is larger than that of the standard example is described.
◯: The temperature range in which the tan δ of the example or comparative example is larger than the standard example is 200 ° C. or more Δ: The temperature range in which the tan δ of the example or comparative example is larger than the standard example is 100 ° C. or more and less than 200 ° C. ×: From the standard example The temperature range in which the tan δ of the Examples or Comparative Examples is large is less than 100 ° C

<Energy absorption capacity>
The tan δ in the rubber elasticity region (in steps of 10 ° C. in the region above the Tg peak temperature) was evaluated based on the DMA measurement results. The maximum value of tan δ (Example or Comparative Example) / standard example tan δ is shown.
◯: The maximum value of tan δ (example or comparative example) / standard example tan δ is 4.0 or more Δ: tan δ (example or comparative example) / maximum value of standard example tan δ is 2.0 or more and less than 4.0 x: The maximum value of tan δ (Example or Comparative Example) / standard example tan δ is less than 2.0.

<Comprehensive evaluation>: Judged by temperature range x energy absorption capacity.
○: When temperature range × energy absorption capacity is “○” × “○” △: Temperature range × energy absorption capacity is “△” × “○”, “○” × “△” or “△” × “△” X: When there is “x” in either temperature range or energy absorption capacity

  Examples 1 to 12 are examples of the present invention, in which a modifier, a urethane resin (urethane prepolymer), and a curing agent are mixed and heated to produce a sheet that is a molded body. In Examples 1 to 11, in the rubber elastic region (the region of Tg or more of the urethane elastomer formed from the urethane resin (urethane prepolymer) and the curing agent), the standard example 1 or 2 containing no modifier as the raw material was used. In comparison, the tan δ value was large in a wider temperature range. Further, the maximum value of tan δ in Examples 1 to 8 was twice or more the maximum value of tan δ in Standard Example 1 or 2. From this result, it became clear that the use of the modifier of the present invention makes it possible to enhance the shock absorbing performance and to widen the temperature range in which the shock can be absorbed. As shown in FIG. 1, in the rubber elasticity region, the tan δ value of the example shows a value larger than the tan δ value of the standard example.

  On the other hand, Comparative Examples 1 and 2 are examples in which the modifier having no group represented by the formula (1) was used, and it cannot be said that the impact absorption performance and the temperature range capable of absorbing impact are sufficient. It was

Claims (5)

Having a reactive group X and a dangling chain at the end,
A modifier having an energy absorption index of more than 1 measured by the following method.
[Measurement method of energy absorption index]
(1) The amount of the dangling chain in the total of the modifier and the standard polymer having the same main chain skeleton as the modifier and the reactive group X. Is mixed so as to be 0.03 mol / kg or more and 0.08 mol / kg or less.
(2) The mixture and the curing agent having a group Y capable of reacting with the reactive group X have a mass ratio of the mixture and the curing agent (mass of mixture / mass of curing agent) represented by the following formula. It mixes so that it may become a value represented, and it hardens, and hardened | cured material C1 is obtained.
Mass of mixture / mass of curing agent = 1.05 × (group X equivalent of mixture / group Y equivalent of curing agent)
(3) The dynamic mechanical properties of the cured product C1 are measured according to JIS K 7244, and the minimum tan δ value in the rubber elastic region in the obtained tan δ spectrum is tan δ ₁ .
(4) Separately, 100 parts by mass of the standard polymer and the curing agent, and the mass ratio of the standard polymer and the curing agent (mass of standard polymer / mass of curing agent) are represented by the following formulas: To obtain a cured product C0.
Mass of standard polymer / mass of curing agent = 1.05 × (group X equivalent of standard polymer / group Y equivalent of curing agent)
(5) The dynamic mechanical properties of the cured product C0 are measured according to JIS K 7244, and the minimum tan δ value in the rubber elastic region in the obtained tan δ spectrum is tan δ ₀ .
(6) Let tan δ ₁ / tan δ ₀ be the energy absorption index.   The modifier according to claim 1, which has a number average molecular weight of 250 or more and 10,000 or less.   A resin composition comprising the modifier according to claim 1 or 2 and an organic polymer.   A resin composition in which the content of the modifier is 0.1% by mass or more and 90% by mass or less.   An article formed from the resin composition according to claim 4.

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