Antistatic agent

Abstract

The present invention provides an antistatic agent that is excellent in antistatic effects and, when compounded, excellent in appearance of a molded product.　An antistatic agent according to the present invention contains (A) an amine compound and (B) an acid. The amine compound (A) is represented by formula (I) or (II). (In the formula, Ra each independently denote a C1-22 linear or branched hydroxyhydrocarbon group having one or more hydroxyl groups; Rb are each independently denote a hydrogen atom or a C1-3 hydrocarbon group; and c denotes an integer of 1-3). (In the formula R1, R2, and R3 each denote a hydrocarbon group or the like). The acid (B) is a phosphoric acid or a carboxylic acid.

Description

Antistatic agent

[0001] This invention relates to an antistatic agent.

[0002] Synthetic resin products have the problem of easily attracting dust due to static electricity, so various antistatic agents have been proposed.

[0003] For antistatic agents used in synthetic resin products, polymer-type antistatic agents such as those described in Patent Documents 1 and 2 have been proposed and are widely used. Methods using low-molecular-weight salts, as described in Patent Documents 3 to 5, have also been proposed.

[0004] However, polymer-type antistatic agents such as those described in Patent Documents 1 and 2 have drawbacks, including poor compatibility with resins and the large amount required to exhibit their effects. As a result, poor dispersion often leads to defects in the appearance of molded products and insufficient antistatic performance.

[0005] Furthermore, the antistatic agents described in Patent Documents 3 and 4 contain fluorine atoms, which are used to increase conductivity by utilizing the strong electron-withdrawing effect of fluorine. However, antistatic agents containing fluorine may decompose due to the effects of heat and other factors. Since the decomposition products corrode metals, antistatic agents containing fluorine atoms are considered undesirable in certain fields.

[0006] Although the antistatic agent described in Patent Document 5 does not contain fluorine, it has limitations in the range of application of resins, and there were still problems with the appearance of the resin into which it was formulated.

[0007] Japanese Patent Publication No. 2000-34330, Japanese Patent Publication No. 2022-503, Japanese Patent Publication No. 2004-217931, Japanese Patent Publication No. 2023-181119, Japanese Patent Publication No. 2006-176648

[0008] This invention has been made in view of the above circumstances, and aims to provide an antistatic agent that has excellent antistatic effect and excellent appearance of molded products during compounding.

[0009] In order to solve the above problems, the present inventors conducted intensive studies and as a result, found that an antistatic agent containing a specific amine compound and an acid provides an antistatic agent with excellent antistatic effect and excellent transparency of the molded product containing the same, thus completing the present invention.

[0010] That is, the antistatic agent of the present invention contains (A) an amine compound and (B) an acid, and (A) the amine compound is represented by the following formula (I) or (II): (In the formula, R a each independently represents a linear or branched hydroxyhydrocarbon group having 1 to 22 carbon atoms and having one or more hydroxyl groups, and R b each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and c represents an integer of 1 to 3.) (In the formula, R 1 represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, and R 2 each independently represents a hydrogen atom or a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, and R 3 represents a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, l represents 0 to 2, m represents 0 to 2, and n represents 0 or 1. R 1 and R 2 may together form a ring having 3 to 22 carbon atoms. X represents a hydrogen atom or a monovalent cation.) And (B) the acid is a phosphoric acid or a carboxylic acid.

[0011] According to the antistatic agent of the present invention, it has an excellent antistatic effect and also has excellent transparency of the molded product containing the same.

[0012] Hereinafter, the embodiments for carrying out the present invention will be specifically described. (Antistatic agent) The antistatic agent of the present invention contains (A) an amine compound and (B) an acid. (A) The amine compound is represented by the following formula (I) or (II).

[0013]

[0014] (In the formula, R a each independently represents a linear or branched hydroxyhydrocarbon group having 1 to 22 carbon atoms and having one or more hydroxyl groups, and R bEach of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and c represents an integer from 1 to 3. (In the formula, R 1 R represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms, which may have substituents. 2 Each of these independently represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms, which may have a hydrogen atom or a substituent. 3 R represents a divalent hydrocarbon group having 1 to 22 carbon atoms, which may have substituents, where l is 0 to 2, m is 0 to 2, and n is 0 or 1. 1 and R 2 These may combine to form a ring with 3 to 22 carbon atoms. (X represents a hydrogen atom or a monovalent cation.)

[0015] [Hydrogen Groups] In this specification, hydrocarbon groups are not particularly limited, but examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and hydrocarbon groups that combine these. They may be monovalent or polyvalent depending on the context. They basically consist of hydrocarbons, but substituents as described below are permitted as long as the hydrocarbon structure is the main component and does not affect the effects of the present invention. Examples of monovalent saturated or unsaturated aliphatic hydrocarbon groups are not particularly limited, but examples include linear or branched alkyl groups, alkenyl groups, and alkynyl groups having 1 to 22 carbon atoms.

[0016] The saturated or unsaturated alicyclic hydrocarbon group is not particularly limited, but examples include saturated or unsaturated alicyclic hydrocarbon groups having 3 to 22 carbon atoms, with saturated alicyclic hydrocarbon groups being preferred.

[0017] The aromatic hydrocarbon group is not particularly limited, but examples include aromatic hydrocarbon groups having 6 to 22 carbon atoms, preferably phenyl groups, naphthyl groups, anthracenyl groups, and groups containing aromatic ring residues such as residues thereof. It may also form a fused ring together with substituents such as those described later for oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, and phosphorus-containing groups.

[0018] Examples of divalent hydrocarbon groups include those obtained by removing one hydrogen atom from the above-mentioned groups.

[0019] [Substituents] The above substituents are not particularly limited, but examples include hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, halogens, etc. Substituents also include groups to which these substituents are bonded.

[0020] The oxygen-containing group is not particularly limited, but examples include hydroxyl group-containing groups, alkoxy group-containing groups, acetoxy group-containing groups, acetyl group-containing groups, aldehyde group-containing groups, carboxyl group-containing groups, carboxylate group-containing groups, urea group-containing groups, urethane group-containing groups, amide group-containing groups, imide group-containing groups, ether group-containing groups, carbonyl group-containing groups, ester group-containing groups, oxazole group-containing groups, morpholine group-containing groups, carbamate group-containing groups, carbamoyl group-containing groups, polyoxyethylene group-containing groups, tocopheryl group-containing groups, chroman group-containing groups, dihydropyran group-containing groups, glyceryl group-containing groups, and glyceryl ether group-containing groups. The number of carbon atoms in the oxygen-containing group is not particularly limited, but for example, it is 0 to 22.

[0021] The nitrogen-containing group is not particularly limited, but examples include cyano group-containing groups, cyanato group-containing groups, isocyanate group-containing groups, nitro group-containing groups, nitroalkyl group-containing groups, amide group-containing groups, guanidino group-containing groups, imidazolyl group-containing groups, indolyl group-containing groups, urea group-containing groups, urethane group-containing groups, imide group-containing groups, carbodiimide group-containing groups, azo group-containing groups, pyridine group-containing groups, imidazole group-containing groups, primary amino group-containing groups, secondary amino group-containing groups, tertiary amino group-containing groups, quaternary ammonium group-containing groups, aminoalkyl group-containing groups, etc. The number of carbon atoms in the nitrogen-containing group is not particularly limited, but for example, it is 0 to 22.

[0022] The sulfur-containing groups are not particularly limited, but examples include sulfate-containing groups, sulfonyl-containing groups, sulfonic acid-containing groups, mercapto-containing groups, thioether-containing groups, thiocarbonyl-containing groups, thiourea-containing groups, thiocarboxy-containing groups, thiocarboxylate-containing groups, dithiocarboxylate-containing groups, dithiocarboxylate-containing groups, sulfate-containing groups, thiophene-containing groups, thiazole-containing groups, thiol-containing groups, sulfo-containing groups, sulfide-containing groups, disulfide-containing groups, thioester-containing groups, thioamide-containing groups, thiocarbamate-containing groups, and dithiocarbamate-containing groups. The number of carbon atoms in the sulfur-containing group is not particularly limited, but for example, it is 0 to 22.

[0023] The phosphorus-containing group is not particularly limited, but examples include phosphate group-containing groups, phosphite group-containing groups, phosphonic acid group-containing groups, phosphinic acid group-containing groups, phosphonitic acid group-containing groups, phosphinic acid group-containing groups, pyrophosphate group-containing groups, phosphate ester group-containing groups, phosphite ester group-containing groups, phosphonic acid ester group-containing groups, pyrophosphate group-containing groups, and their ester groups. The number of carbon atoms in the phosphorus-containing group is not particularly limited, but for example, it is 0 to 22.

[0024] The oxygen-containing group, nitrogen-containing group, sulfur-containing group, and phosphorus-containing group may have a hydrocarbon moiety, and their number of carbon atoms is, for example, 1 to 22.

[0025] Examples of halogens include fluorine, chlorine, bromine, and iodine.

[0026] In the above formula (I), R a The hydrocarbon group in the hydroxy hydrocarbon group is not particularly limited, but examples include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. Among these, saturated aliphatic hydrocarbon groups are preferred.

[0027] R a The hydroxy hydrocarbon group is either a monohydroxy hydrocarbon group having one hydroxyl group, or a polyhydroxy hydrocarbon group having two or more hydroxyl groups.

[0028] R aWhen the group is a monohydroxy hydrocarbon group, it may be linear or branched, but linear is preferred. The number of carbon atoms in the monohydroxy hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3.

[0029] The monohydroxy hydrocarbon group is not particularly limited, but examples include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropan-1-yl group, 2-hydroxypropan-1-yl group, 3-hydroxypropan-1-yl group, 1-hydroxybutan-1-yl group, 2-hydroxybutan-1-yl group, 3-hydroxybutan-1-yl group, 4-hydroxybutan-1-yl group, 5-hydroxypentan-1-yl group, 6-hydroxyhexane-1-yl group, and the like.

[0030] R a When the group is a polyhydroxy hydrocarbon group, it may be linear or branched, but branched is preferred. The number of carbon atoms in the branched polyhydroxy hydrocarbon group is preferably 3 to 18, more preferably 3 to 12, even more preferably 3 to 8, and particularly preferably 3 to 6. The number of hydroxyl groups per carbon atom in the branched polyhydroxy hydrocarbon group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 3. The number of carbon atoms in the linear polyhydroxy hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. The number of hydroxyl groups per carbon atom in the linear polyhydroxy hydrocarbon group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 3.

[0031] The branched polyhydroxy hydrocarbon group is not particularly limited, but examples include dihydroxypropan-2-yl groups such as 1,2-dihydroxypropan-2-yl group and 1,3-dihydroxypropan-2-yl group; trihydroxypropan-2-yl group; dihydroxy-2-methylpropan-2-yl groups such as 1,3-dihydroxy-2-methylpropan-2-yl group; trihydroxy-2-methylpropan-2-yl groups such as 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group; dihydroxy-2-ethylpropan-2-yl groups such as 1,3-dihydroxy-2-ethylpropan-2-yl group; trihydroxy-2-ethylpropan-2-yl group; 1,2-dihydroxy-2-methylpropan-1-yl group, 1,3-dihydroxy-2-methylpropan-1-yl group, 2,3-dihydroxy Examples include dihydroxy-2-methylpropan-1-yl groups such as xy-2-methylpropan-1-yl group; trihydroxy-2-methylpropan-1-yl group; tetrahydroxy-2-methylpropan-1-yl group; dihydroxybutan-2-yl groups such as 1,2-dihydroxybutan-2-yl group, 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutan-2-yl group, 2,3-dihydroxybutan-2-yl group, 2,4-dihydroxybutan-2-yl group, and 3,4-dihydroxybutan-2-yl group; trihydroxybutan-2-yl groups such as 1,2,3-trihydroxybutan-2-yl group, 1,2,4-trihydroxybutan-2-yl group, 1,3,4-trihydroxybutan-2-yl group, and 2,3,4-trihydroxybutan-2-yl group; and tetrahydroxybutan-2-yl group. Among these, branched polyhydroxyalkyl groups represented by the following formula are exemplified as preferred. (In the formula, R 11 (wherein represents a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a linear monohydroxyalkyl group having 1 to 4 carbon atoms.) Specifically, examples include 1,3-dihydroxypropan-2-yl group, 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, and 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group.

[0032] The linear polyhydroxy hydrocarbon group is not particularly limited, but examples include dihydroxyethyl groups such as 1,2-dihydroxyethyl group; dihydroxypropan-1-yl groups such as 1,2-dihydroxypropan-1-yl group and 2,3-dihydroxypropan-1-yl group; trihydroxypropan-1-yl group; and dihydroxybutan-1-yl groups such as 1,2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group, 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4-dihydroxybutan-1-yl group, and 3,4-dihydroxybutan-1-yl group. Examples include trihydroxybutan-1-yl groups such as 1,2,3-trihydroxybutan-1-yl group, 1,2,4-trihydroxybutan-1-yl group, 1,3,4-trihydroxybutan-1-yl group, and 2,3,4-trihydroxybutan-1-yl group; tetrahydroxybutan-1-yl group; di, tri, tetra, or pentahydroxypentan-1-yl group; di, tri, tetra, penta, or hexahydroxyhexane-1-yl group; di, tri, tetra, penta, hexa, or heptahydroxyheptan-1-yl group; and di, tri, tetra, penta, hexa, hepta, or octahydroxyoctan-1-yl group.

[0033] In the above formula (I), R b Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Among them, R b A hydrogen atom is preferred. b In this context, the hydrocarbon group is not particularly limited, but examples include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. Among these, saturated aliphatic hydrocarbon groups are preferred. b In this, the hydrocarbon group may be linear or branched. The hydrocarbon group preferably has 1 or 2 carbon atoms. b Examples of hydrocarbon groups include methyl, ethyl, n-propyl, and isopropyl groups.

[0034] In formula (I) above, c represents an integer from 1 to 3. c is preferably 1 or 3, and more preferably 3.

[0035] Examples of the (A) amine compound represented by formula (I) include 2,2',2''-nitrilotriethanol, 2-aminoethanol, 2-dimethylaminoethanol, 2,2'-dihydroxydiethylaminediethanolamine, and 2-amino-2-ethyl-1,3-propanediol. Among these, 2,2',2''-nitrilotriethanol, 2-aminoethanol, and 2-dimethylaminoethanol are preferred.

[0036] In the above formula (II), R 1 R represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms, which may have substituents. 2 Each of these independently represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms, which may have a hydrogen atom or a substituent. 1 and R 2 These may combine to form a ring having 3 to 22 carbon atoms. The hydrocarbon group is as described in the [Hydrogen Group] section above. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group (alkyl group). The alkyl group may be, for example, linear or branched with 1 to 22, 1 to 10, or 1 to 5 carbon atoms.

[0037] The substituents mentioned above are not particularly limited, but examples include those listed in the [Substituents] section above. Among the substituents, those having oxygen-containing groups, nitrogen-containing groups, or sulfur-containing groups are preferred, and oxygen-containing groups are more preferred. Among the substituents, hydroxyl-containing groups, carboxyl-containing groups, carboxylate-containing groups, ester-containing groups, ether-containing groups, alkoxy-containing groups, amino-containing groups, amide-containing groups, guanidino-containing groups, imidazolyl-containing groups, indolyl-containing groups, mercapto-containing groups, and thioether-containing groups are preferred, hydroxyl-containing groups, carboxyl-containing groups, carboxylate-containing groups, amino-containing groups, and guanidino-containing groups are more preferred, hydroxyl-containing groups and carboxyl-containing groups are even more preferred, and hydroxyl-containing groups are particularly preferred.

[0038] The hydrocarbon group described above may contain an oxygen-containing group. In this invention, "the hydrocarbon group contains an oxygen-containing group" includes cases in which the hydrocarbon moiety is interrupted by the oxygen-containing group, the group is included at the base end, or a hydrogen atom is substituted by the group.

[0039] Note R 1 and R 2 The fact that they come together to form a ring with 3 to 22 carbon atoms means that R 1 l NH m CR 2 In units of R 1 and R 2 together R 1 , R 2 This means that the ring containing nitrogen N has a total number of carbon atoms forming the C ring of 3 to 22, preferably 4 to 10. In addition to the 3 to 22 carbon atoms forming the ring, the ring may also have substituents such as monovalent or divalent hydrocarbon groups, sulfur-containing groups, nitrogen-containing groups, and oxygen-containing groups having 1 to 22, preferably 1 to 10, more preferably 1 to 3 carbon atoms. Preferably, R 1 , R 2 The ring contains nitrogen atoms with a total of 4 to 10 carbon atoms forming a C ring, and the ring does not have substituents.

[0040] In formula (II) above, l is preferably 0 or 1, and m is preferably 1 or 2.

[0041] In the above formula (II), R 3 n is a divalent hydrocarbon group having 1 to 22 carbon atoms, which may have substituents. The hydrocarbon group is a divalent group, as described in the [Hydrogen Group] section above. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group (alkylene group). The alkylene group may be linear or branched, for example, having 1 to 22, 1 to 10, or 1 to 5 carbon atoms. In formula (II) above, n is preferably 0.

[0042] The above hydrocarbon group may have substituents, and there are no particular limitations on the substituents, but examples include those listed in the [Substituents] column above.

[0043] When component (A) is represented by the above formula (II), an amino acid in which X is a hydrogen atom is preferred.

[0044] In the compound represented by formula (II) above, the amino acid includes compounds having one or more amino groups (primary amino groups, secondary amino groups, or tertiary amino groups) and one or more carboxyl groups (-COOH) in one molecule. However, amino acids having an amide group, urea group, urethane group, or guanidino group have at least one amino group in addition to these groups.

[0045] R 2 Is it a hydrogen atom, or R 2 As for amino acids having alkyl chains, R 2 Examples include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. In this case, l is either 0 or l is 1 and R 1 It is preferable that n is a linear or branched alkyl group having 1 to 3 carbon atoms. It is also preferable that n is 0. Specific examples of such amino acids include glycine, alanine, valine, leucine, isoleucine, and sarcosine.

[0046] R 2 Amino acids that have a hydroxyl group include R 2 Examples include a linear or branched structure having 1 to 5 carbon atoms, preferably 1 to 3, and a hydroxyalkyl group having 1 to 3 hydroxyl groups, preferably 1. In this case, l is either 0 or l is 1 and R 1 It is preferable that the element is a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include serine and threonine.

[0047] R 2 As for amino acids containing sulfur, R 2 The following are some examples:

[0048]

[0049] (In the formula, R 21 R indicates a methylene group, 22R represents a methyl group or -CH2CH(NH2)(COOH). a1 represents 1 to 5, preferably 1 to 3, and a2 represents 1 to 4, preferably 1 or 2. a1 has R 21 The order of the two S's is arbitrary, but R 21 The elements are arranged alternately with -S-, and the base end is R 21 And R 22 The group that binds to it is preferably -S-.

[0050] In this case, l is either 0 or l is 1 and R 1 It is preferable that the element is a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include cysteine, methionine, and cystathionine.

[0051] R 2 Amino acids that have an amide group include R 2 The following are some examples:

[0052] (In the formula, R 23 (This represents a linear or branched alkylene group having 1 to 5 carbon atoms, preferably 1 or 2 carbon atoms.)

[0053] In this case, l is either 0 or l is 1 and R 1 It is preferable that the group is a linear or branched alkyl group having 1 to 3 carbon atoms and containing a secondary amino group, and more preferably that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include asparagine, glutamine, and citrulline.

[0054] R 2 Amino acids that have an imino group include N and R 1 Examples include compounds in which these elements combine to form a heterocycle. 1 This represents a C3 or C4 alkylene group which may have a hydroxyl group, forming a pyrrolidine ring or a piperidine ring. Preferably, it forms a pyrrolidine ring. In this case, it is preferable that l is 1. Also, it is preferable that n is 0. Specific examples of such amino acids include proline and hydroxyproline.

[0055] R 2 Amino acids that have an aromatic group include R 2 The following are some examples:

[0056]

[0057] (In the formula, R 24 R represents a linear or branched alkylene group having 1 to 5 carbon atoms, preferably 1 or 2 carbon atoms. 25 (This represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic group having 3 to 10 carbon atoms, which may have substituents.) 25 Preferably, it represents a phenyl group, a hydroxyphenyl group, or an indole group.

[0058] In this case, l is either 0 or l is 1 and R 1 is a linear or branched alkyl group having 1 to 3 carbon atoms, or l is 1 and R 1 It is preferable that the group has 2 to 4 carbon atoms and contains an amide group and a secondary amino group, and it is more preferable that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include phenylalanine, tyrosine, tryptophan, histidine, 1-methylhistidine, 3-methylhistidine, anserine, and carnosine.

[0059] As for β, γ, δ, or ε-amino acids, R 3 Examples include linear or branched alkylene groups having 1 to 4 carbon atoms. In this case, l is either 0 or l is 1 and R 1 It is preferable that the group is a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably that l is 0. It is also preferable that n is 1. Specific examples of such amino acids include β-alanine, β-aminoisobutyric acid, γ-aminobutyric acid, and ε-aminocaproic acid.

[0060] R 2 Examples of amino acids that contain a carboxyl group are those represented by the following formula.

[0061] (In the formula, R 26(This represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.)

[0062] In this case, l is either 0 or l is 1 and R 1 It is preferable that the element is a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include aspartic acid, glutamic acid, and α-aminoadipic acid.

[0063] In addition to the above, R 2 Examples of those that can be expressed by the following formula include:

[0064]

[0065] (In the formula, R 27 R represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have a hydroxyl group. 28 (This indicates -NH2, -NHC (=NH)(NH2), or an imidazolyl group.)

[0066] In this case, l is either 0 or l is 1 and R 1 It is preferable that the element is a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably that l is 0. It is also preferable that n is 0. Specific examples of such amino acids include arginine, lysine, histidine, 5-hydroxylysine, and ornithine.

[0067] Among these, a preferred example of the (A) amine compound represented by formula (II) is R such as arginine. 2 ga-R 27 -R 28 The amino acid represented by R 2 Glycine, which contains hydrogen atoms, is one example.

[0068] In the present invention, (B) acid is a phosphoric acid or a carboxylic acid. Examples of the phosphoric acids include phosphinic acid, phosphonic acid, phosphoric acid, and phosphoric acid esters, but phosphinic acid, phosphonic acid, and phosphoric acid are preferred from the viewpoint of antistatic properties and compatibility with resins.

[0069] The carboxylic acid is a carboxylic acid having at least one carboxyl group (-COOH) in its molecule. The carboxylic acid may also have an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, a hydrocarbon group, etc., and may be a carboxylate group formed by the dissociation of a hydrogen atom from a carboxyl group. A carboxylic acid having a hydrocarbon group is preferred. Although not particularly limited, examples of carboxylic acids having a hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, or aromatic hydrocarbon groups, or combinations thereof having a hydrocarbon group and a carboxyl group. Examples include saturated aliphatic carboxylic acids, unsaturated aliphatic carboxylic acids, saturated or unsaturated alicyclic carboxylic acids, aromatic carboxylic acids, saturated aliphatic hydroxycarboxylic acids, unsaturated aliphatic hydroxycarboxylic acids, saturated or unsaturated alicyclic hydroxycarboxylic acids, aromatic hydroxycarboxylic acids, carbonyl carboxylic acids, alkyl ether carboxylic acids, halogenated carboxylic acids, etc. (The number of carbon atoms in the carboxylic acids listed below includes the carbon atoms of the carboxyl group.)

[0070] Saturated aliphatic carboxylic acids consist of a linear or branched saturated aliphatic hydrocarbon group and one or more carboxyl groups, preferably having 1 to 22 carbon atoms. Examples of saturated aliphatic carboxylic acids include saturated aliphatic monocarboxylic acids with one carboxyl group and saturated aliphatic dicarboxylic acids with two carboxyl groups. Saturated aliphatic monocarboxylic acids consist of a linear or branched saturated aliphatic hydrocarbon group and one carboxyl group, preferably having 1 to 22 carbon atoms. Among these, saturated aliphatic monocarboxylic acids having 12 to 22 carbon atoms are preferred, and branched saturated aliphatic monocarboxylic acids are more preferred. Specifically, although not particularly limited, examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, henicosyl acid, behenic acid, isobutyric acid, 2-methylbutyric acid, isovaleric acid, 2-ethylhexanoic acid, isononanoic acid, isopalmitic acid, isostearic acid, etc. Saturated aliphatic dicarboxylic acid consists of a linear or branched saturated aliphatic hydrocarbon group and two carboxyl groups, and preferably has 2 to 22 carbon atoms. Among these, HOOC(CH2) b1 A saturated dicarboxylic acid represented by COOH (where b1 is an integer from 0 to 4) is preferred. Specifically, although not particularly limited, examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and glutamic acid.

[0071] Unsaturated aliphatic carboxylic acids consist of a linear or branched unsaturated aliphatic hydrocarbon group and one or more carboxyl groups, preferably having 3 to 22 carbon atoms. Examples of unsaturated aliphatic carboxylic acids include unsaturated aliphatic monocarboxylic acids with one carboxyl group and unsaturated aliphatic dicarboxylic acids with two carboxyl groups. Unsaturated aliphatic monocarboxylic acids consist of a linear or branched unsaturated aliphatic hydrocarbon group and one carboxyl group, preferably having 1 to 22 carbon atoms. Among these, unsaturated aliphatic monocarboxylic acids having 12 to 22 carbon atoms and having 1 to 4 carbon-carbon double bonds (unsaturated bonds) are preferred. Specifically, although not particularly limited, examples include acrylic acid, methacrylic acid, crotonic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, and arachidonic acid. Unsaturated aliphatic dicarboxylic acids consist of a linear or branched unsaturated aliphatic hydrocarbon group and two carboxyl groups, preferably having 1 to 4 carbon atoms. Specifically, although not limited to these examples, maleic acid, fumaric acid, and others can be cited.

[0072] Saturated or unsaturated alicyclic carboxylic acids consist of a saturated or unsaturated carbon ring that does not have aromaticity and one or more carboxyl groups, preferably having 3 to 20 carbon atoms. Among these, saturated alicyclic carboxylic acids having a cyclohexane ring skeleton are preferred. Examples of saturated or unsaturated alicyclic carboxylic acids include saturated or unsaturated alicyclic monocarboxylic acids with one carboxyl group, and saturated or unsaturated alicyclic dicarboxylic acids with two carboxyl groups. Examples of saturated or unsaturated alicyclic monocarboxylic acids are not particularly limited, but include cyclohexanecarboxylic acid. Examples of saturated or unsaturated alicyclic dicarboxylic acids are not particularly limited, but include cyclohexanedicarboxylic acid.

[0073] An aromatic carboxylic acid consists of a monocyclic or multiple rings with aromaticity and one or more carboxy groups, and preferably has 6 to 20 carbon atoms. Among them, an aromatic carboxylic acid having a benzene ring skeleton is preferred. Examples of the aromatic carboxylic acid include an aromatic monocarboxylic acid having one carboxy group, an aromatic dicarboxylic acid having two carboxy groups, and the like. The aromatic monocarboxylic acid is not particularly limited, and examples thereof include benzoic acid and cinnamic acid. The aromatic dicarboxylic acid is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and the like.

[0074] A saturated aliphatic hydroxycarboxylic acid consists of a linear or branched saturated aliphatic hydrocarbon group, one or more carboxy groups, and one or more hydroxy groups, and preferably has 2 to 24 carbon atoms. Among them, a saturated aliphatic hydroxycarboxylic acid having 2 to 7 carbon atoms and 1 to 5 hydroxy groups is preferred. Examples of the saturated aliphatic hydroxycarboxylic acid include a saturated aliphatic hydroxymonocarboxylic acid having one carboxy group, a saturated aliphatic hydroxydior tricarboxylic acid having two or three carboxy groups, and the like. The saturated aliphatic hydroxymonocarboxylic acid preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms. The number of hydroxy groups is preferably 1 to 5. Among them, (R 29 )3C(C(R 30 )2)<Q b2 COOH (b2 represents an integer of 1 to 4, and 3 Rs and 2×b2 Rs 29 and 2×b2 Rs 30Each independently represents a hydrogen atom or a hydroxyl group, and the total number of hydroxyl groups is 1 to 5. A saturated hydroxymonocarboxylic acid represented by ( ) is preferred. Specifically, although not particularly limited, for example, glycolic acid, lactic acid, glyceric acid, hydroxyacetic acid, hydroxybutyric acid, 2-hydroxydecanoic acid, 3-hydroxydecanoic acid, 12-hydroxystearic acid, dihydroxystearic acid, cerebronic acid, leucic acid, mevalonic acid, pantothenic acid, gluconic acid, galactonic acid, mannonic acid, arabinonic acid, fructuronic acid, tagaturonic acid, aldonic acid, etc. can be mentioned. The saturated aliphatic hydroxydior tricarboxylic acid preferably has 4 to 22 carbon atoms, more preferably 4 to 10 carbon atoms, and still more preferably 4 to 8 carbon atoms. The number of hydroxyl groups is preferably 1 to 3. Among them, lactic acid is particularly preferred. Among them, HOOC C(R 31 R 32 ), C(R 33 R 34 ), C(R 35 R 36 ), C OOH (R 31 ~R 36 Each independently represents a hydrogen atom, a hydroxyl group, or a carboxy group, the total number of hydroxyl groups is 1 to 2, and the total number of carboxy groups is 2 to 1. A saturated hydroxydicarboxylic acid or a saturated hydroxytricarboxylic acid represented by ( ) is preferred. As the saturated hydroxydicarboxylic acid, although not particularly limited, for example, tartronic acid, malic acid, tartaric acid, citramalic acid, etc. can be mentioned. As the saturated hydroxytricarboxylic acid, although not particularly limited, for example, citric acid, isocitric acid, etc. can be mentioned.

[0075] The unsaturated aliphatic hydroxycarboxylic acid is composed of a linear or branched saturated aliphatic hydrocarbon group, one or more carboxy groups, and one or more hydroxyl groups, and preferably has 3 to 22 carbon atoms. Specifically, although not particularly limited, for example, ricinoleic acid, ricinelaidic acid, etc. can be mentioned.

[0076] Saturated or unsaturated alicyclic hydroxycarboxylic acids consist of a non-aromatic saturated or unsaturated carbon ring, one or more carboxyl groups, and one or more hydroxyl groups, preferably having 4 to 20 carbon atoms. Among these, saturated alicyclic hydroxycarboxylic acids with a 6-membered ring skeleton having 1 to 4 hydroxyl groups are preferred. Specifically, although not particularly limited, examples include hydroxycyclohexanecarboxylic acid, dihydroxycyclohexanecarboxylic acid, quinic acid (1,3,4,5-tetrahydroxycyclohexanecarboxylic acid), shikimic acid, glucuronic acid, galacturonic acid, mannuronic acid, iduronic acid, and guluronic acid. Cyclic lactones having hydroxyl groups can also be preferably used, and specifically, although not particularly limited, examples include ascorbic acid and erythorbic acid.

[0077] Aromatic hydroxycarboxylic acids consist of an aromatic monocyclic or multiple rings, one or more carboxyl groups, and one or more hydroxyl groups, preferably having 6 to 20 carbon atoms. Among these, aromatic carboxylic acids with a benzene ring skeleton having 1 to 3 hydroxyl groups are preferred. Specifically, although not particularly limited, examples include salicylic acid, hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, hydroxymethylbenzoic acid, vanillic acid, syringic acid, protocatechuic acid, gentisic acid, orceric acid, mandelic acid, benzyl acid, atrolactinic acid, floretic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, and synapic acid.

[0078] Carbonyl carboxylic acids are carboxylic acids having 3 to 22 carbon atoms and containing a carbonyl group in the molecule, with carbonyl carboxylic acids having 3 to 7 carbon atoms and containing 1 to 2 carbonyl groups being preferred. Among these, CH3((CH2) b3 CO(CH2) b4 A carbonyl carboxylic acid represented as COOH (where b3 and b4 are integers from 0 to 2) is preferred. Specifically, although not particularly limited, examples include pyruvic acid.

[0079] Alkyl ether carboxylic acids include polyoxyalkylene alkyl ether carboxylic acids, which are carboxylic acids having 2 to 22 carbon atoms and containing an ether group in the molecule, with alkyl carboxylic acids having 2 to 12 carbon atoms and containing 1 to 2 ether groups being preferred. Among these, CH3(CH2) b5 O(CH2) b6 Alkyl ether carboxylic acids and polyoxyethylene alkyl ether carboxylic acids represented by COOH (where b5 and b6 are integers from 0 to 4) are preferred. Specifically, although not particularly limited, examples include methoxyacetic acid, ethoxyacetic acid, methoxybutyric acid, and ethoxybutyric acid.

[0080] As the halogenated carboxylic acid, halogenated carboxylic acids having 2 to 22 carbon atoms are preferred. Specifically, although not particularly limited, examples include halogen-substituted halogenated carboxylic acids such as trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluoropropionic acid, pentachloropropionic acid, pentabromopropionic acid, perfluorononanoic acid, perchlorononanoic acid, and perbromonanoic acid.

[0081] Among the carboxylic acids listed above, saturated aliphatic hydroxycarboxylic acids are preferred from the viewpoint of antistatic properties and the appearance of molded products to which antistatic agents have been applied, saturated aliphatic hydroxy monocarboxylic acids are more preferred, and lactic acid is the most preferred.

[0082] The antistatic agent of the present invention may consist only of (A) an amine compound and (B) an acid, or it may be in the form of a composition. If the antistatic agent of the present invention is a composition, (A) the amine compound and (B) the acid may be mixed first and then incorporated into the composition, or (A) the amine compound and (B) the acid may be mixed simultaneously or separately at any point in the preparation of the composition.

[0083] In addition to (A) amine compounds and (B) acids, the antistatic agent of the present invention may contain other components as long as they do not impair the effects of the present invention. The other components are not particularly limited, but examples include solvents, surfactants, wetting agents, defoaming agents, surface tension modifiers, chelating agents, pH adjusters, rust inhibitors, preservatives, fungicides, antioxidants, oxygen absorbers, and the like.

[0084] The solvent is not particularly limited, but examples include water and organic solvents. These may be used individually or in combination of two or more. As the organic solvent, water-soluble organic solvents and oil-soluble organic solvents can be used.

[0085] The water-soluble organic solvent is not particularly limited, but examples include alcohol-based solvents such as glycerin, methanol, ethanol, isopropyl alcohol, propanol, butanol, and pentanol; glycol-based solvents such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and acetone.

[0086] The oil-soluble organic solvent is not particularly limited, but examples include isoparaffins, hydrocarbon solvents such as toluene, methyl ethyl ketone, and ethyl acetate.

[0087] When the antistatic agent of the present invention is a composition, the amounts of (A) the amine compound and (B) the acid are not particularly limited, but are preferably 50% by mass or more, and more preferably 90% by mass or more. When (A) the amine compound and (B) the acid form an organic ammonium salt in the antistatic agent of the present invention, it is non-volatile, and the volatilization of (A) the amine compound and (B) the acid is suppressed. Therefore, even at high concentrations, there is no odor of (A) the amine compound and (B) the acid, making it useful as an antistatic agent.

[0088] In the antistatic agent of the present invention, the molar ratio of the blended compounds calculated based on the functional groups of (A) the amine compound and (B) the acid is not particularly limited, but can be, for example, 0.1:1 to 10:1. Preferably, it is 0.5:1 to 2:1, more preferably 1:2 to 1:1, and even more preferably 1:1, from the viewpoint of suppressing odor. The molar ratio of the blended compounds calculated based on the functional groups is calculated by multiplying the number of amino groups in one molecule of (A) the amine compound and the valency of (B) the acid by the actual number of moles. From the viewpoint of odor suppression, salt formation is essential, and in this case, it is necessary to consider the number of functional groups involved in salt formation in (A) the amine compound and (B) the acid, so this concept is used.

[0089] In the antistatic agent of the present invention, preferred combinations of (A) an amine compound and (B) an acid include the following examples: • (A) the amine compound is 2,2',2''-nitrilotriethanol, 2-aminoethanol, 2-dimethylaminoethanol, or 2-amino-2-hydroxymethyl-1,3-propanediol, and (B) the acid is phosphinic acid, with a molar ratio of 1:1. • (A) the amine compound is glycine or arginine, and (B) the acid is phosphinic acid, with a molar ratio of 1:1. • (A) the amine compound is 2,2',2''-nitrilotriethanol, and (B) the acid is lactic acid, with a molar ratio of 1:1. • (A) the amine compound is 2-aminoethanol, and (B) the acid is phosphonic acid, with a molar ratio of 2:1. The molar ratio of the compound calculated based on the functional groups is 1:1. (A) The amine compound is 2-aminoethanol, and (B) the acid is phosphoric acid, with a molar ratio of 3:1. The molar ratio of the compound calculated based on the functional groups is 1:1.

[0090] The antistatic agent of the present invention is preferable if it is liquid at room temperature (25°C) because it has excellent compatibility with resins, particularly hydrophilic resins, and is easy to mix uniformly. If the formulation consists only of (A) an amine compound and (B) an acid, it may be used alone if it is liquid at room temperature, or a solvent may be used to make the antistatic agent of the present invention liquid at room temperature.

[0091] The antistatic agent of the present invention is preferably free of fluorine atoms, as the decomposition products produced when it decomposes due to heat or other factors are less likely to corrode metals if it does not contain fluorine atoms.

[0092] The antistatic agent of the present invention is used by applying it to a substrate to be prevented from becoming statically charged. The substrate is not particularly limited, but examples include resin molded articles, textile products, paper, and the like.

[0093] The shape of the resin molded body is not particularly limited and can be in the form of a film, sheet, or three-dimensional object.

[0094] Textile products are not particularly limited, but examples include knitted fabrics, nonwoven fabrics, felts, cords, and yarns made from synthetic fibers such as nylon, polyester, polyacrylonitrile, and polyolefin, semi-synthetic fibers such as triacetate, or fibers blended with natural fibers such as cotton, wool, and silk.

[0095] The paper is not particularly limited, but examples include paper made from pulp, or synthetic paper made from synthetic fibers or chemical fiber materials such as rayon, acetate, or vinyl acetate.

[0096] The antistatic agent of the present invention is not particularly limited in its application to the substrate, but examples include internal addition by adding it to the material of the substrate, and external addition by adding it to the surface of the substrate.

[0097] Methods of internal addition are not particularly limited, but include, for example, dissolving or dispersing the base material in a liquid obtained by dissolving or dispersing it in a solvent, or kneading the base material into a molding material melted in an extruder or the like.

[0098] Methods of external addition are not particularly limited, but include, for example, coating, dipping, spraying, and vapor deposition onto the substrate.

[0099] Among these, internal addition is preferred because it results in excellent appearance, particularly transparency, of the substrate when the antistatic agent of the present invention is added.

[0100] As a material for the substrate to which the antistatic agent of the present invention is added, a hydrophilic resin, and among them a water-soluble resin, is preferred because it can be a substrate with excellent appearance, particularly transparency.

[0101] A hydrophilic resin is a resin that has hydrophilic groups. Preferred hydrophilic groups are functional groups that ionize in water or that hydrate through hydrogen bonding without ionizing. Specifically, hydrophilic groups include hydrogen-bonding functional groups. Hydrogen-bonding functional groups are not particularly limited, but examples include the oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, etc.

[0102] Among these, carboxyl groups, hydroxyl groups, amino groups, amide groups, sulfate groups, sulfonic acid groups, and oxyalkylene groups are preferred as hydrogen-bonding functional groups in hydrophilic resins. Of these, acid groups may be their salts.

[0103] The hydrophilic resin is preferably one in which the hydrophilic group content in the resin is 0.1 mmol / kg or more, more preferably 0.2 mmol / kg or more. It is also preferably 1000 mmol / kg or less, more preferably 100 mmol / kg or less, and even more preferably 10 mmol / kg or less.

[0104] Alternatively, as a hydrophilic resin, from the viewpoint of the monomer from which it is derived, it is preferable that the proportion of hydrophilic groups expressed as (molecular weight of hydrophilic groups in the monomer constituting the resin) / (molecular weight of the monomer) is 20% or more, more preferably 30% or more. Furthermore, it is preferable that it be 80% or less, and more preferably 70% or less.

[0105] In addition to being used as is, hydrophilic resins can be used as a solution dissolved in an aqueous solvent or as an aqueous emulsion dispersed in an aqueous solvent. From the viewpoint of compatibility with the antistatic agent of the present invention, water-soluble resins are preferred among hydrophilic resins. Examples of water-soluble resins include resins that dissolve in 1 part by mass or more in 100 parts by mass of water at normal pressure and room temperature.

[0106] Examples of hydrophilic resins include polyvinylpyrrolidone resins such as polyvinylpyrrolidone; vinyl alcohol resins such as polyvinyl alcohol and polyethylene vinyl alcohol; cellulose resins such as cellulose, cellulose acetate, carboxymethylcellulose, cellulose triacetate, methylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose; gelatin, starch, and casein; polyethylene glycol resins such as polyethylene glycol and polyethylene oxide; polyethylene glycol resins such as polyethylene glycol and polyethylene oxide; polyacrylic acid, sodium polyacrylate, sodium polyvinyl sulfonate, polystyrene sulfonic acid, and polyacrylamide resins; acrylic polymers having at least one selected from polyoxyalkylene chains, amide groups, hydroxyl groups, and acid groups; polyvinyl formal, polyvinyl acetal, polyvinyl butyral, and water-soluble nylon resins (water-soluble polyamide resins).

[0107] The antistatic agent of the present invention can be added to a hydrophilic resin, for example, by adding it to a solution obtained by dissolving or dispersing the hydrophilic resin in an aqueous solvent. The amount of the antistatic agent of the present invention added is not particularly limited, but from the viewpoint of imparting antistatic properties, it is preferably 0.1% by mass or more, and more preferably 1% by mass or more, relative to the total amount of the hydrophilic resin. Furthermore, from the viewpoint of preventing deterioration of the physical properties of the resin, it is preferably 20% by mass or less, and more preferably 10% by mass or less.

[0108] The surface resistance of a substrate to which the antistatic agent of the present invention is applied is not particularly limited depending on the substrate, its material, and purpose, but from the viewpoint of preventing the generation of static electricity, adhesion and contamination of foreign matter, etc., is 5.0 × 10 12 Preferably, Ω / □ or less, and 9.9 × 10 11 A value of Ω / □ or less is more preferable. The lower limit of surface resistance is not particularly limited, but from the viewpoint of the physical properties of the substrate, etc., 1.0 × 10 7 Ω / □ or greater is preferable.

[0109] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0110] <Resin (a)> The following resins a-1 and a-2 were used as resin (a) in the examples and comparative examples. a-1: Polyvinylpyrrolidone Polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Hydrophilic group content in resin: approximately 0.3 mmol / kg, percentage of hydrophilic groups in monomer: 38% a-2: Polyacrylic acid Polyacrylic acid (molecular weight 1,000,000 to 1,600,000) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Hydrophilic group content in resin: approximately 0.5 mmol / kg, percentage of hydrophilic groups in monomer: 63% a-3: Polyvinyl alcohol Kuraray Poval 25-88KL manufactured by Kuraray Co., Ltd. Hydrophilic group content in resin: approximately 5 mmol / kg, percentage of hydrophilic groups in monomer: 41% a-4: Acrylic resin Aqueous dispersion of acrylic resin with the following composition: Butyl acrylate / methyl methacrylate / 2-hydroxyethyl acrylate / acrylic acid = 52 / 43 / 3 / 2 Content of hydrophilic groups in the resin: approximately 0.6 mmol / kg, percentage of hydrophilic groups in the monomer: 39% <Antistatic agent (b)> The following compounds b-1 to b-9 were used as antistatic agents in the examples. (Synthesis of compound b-1) In a 200 mL beaker equipped with a magnetic stirrer, (B) 50% phosphinic acid solution (31.76 g, 0.24 mol), (A) 2,2',2''-nitrilotriethanol (TEA) (35.90 g, 0.24 mol), and ion-exchanged water (35.90 g) were charged and stirred at room temperature for 30 minutes to obtain a 50% concentration phosphinic acid TEA salt (compound b-1).

[0111] (Synthesis of compound b-2) (A) Using the same synthesis method and molar ratio as for b-1, except that TEA was replaced with 2-aminoethanol (MEA), a 50% concentration phosphinate MEA salt (compound b-2) was obtained.

[0112] (Synthesis of compound b-3) (A) A 50% concentration phosphonate DMEA salt (compound b-3) was obtained using the same synthesis method and molar ratio as b-1, except that TEA was replaced with 2-dimethylaminoethanol (DMEA).

[0113] (Synthesis of compound b-4) (B) A 50% lactic acid TEA salt (compound b-4) was obtained using the same synthesis method and molar ratio as b-1, except that the 50% phosphinic acid solution was replaced with lactic acid.

[0114] (Synthesis of compound b-5) (A) The same synthesis method and molar ratio as for b-1 was used, except that TEA was replaced with 2-amino-2-hydroxymethyl-1,3-propanediol (Tris), to obtain a 50% concentration Tris phosphinate salt (compound b-5).

[0115] (Synthesis of compound b-6) (A) Using the same synthesis method and molar ratio as for b-1, except that TEA was replaced with glycine, a 50% concentration glycine phosphinate salt (compound b-6) was obtained.

[0116] (Synthesis of compound b-7) (A) Using the same synthesis method and molar ratio as for b-1, except that TEA was replaced with arginine, a 50% concentration phosphinate arginine salt (compound b-7) was obtained.

[0117] (Synthesis of compound b-8) (B) A 50% phosphonic acid MEA salt (compound b-8) was obtained by the same synthesis method as b-2, except that the 50% phosphinic acid solution was replaced with phosphonic acid and the molar ratio of phosphonic acid to MEA was 1:2.

[0118] (Synthesis of compound b-9) (B) The same synthesis method and molar ratio as for b-2 was used, except that the 50% phosphinic acid solution was replaced with phosphoric acid and the molar ratio of phosphoric acid to MEA was 1:3, to obtain a 50% concentration phosphoric acid MEA salt (compound b-9).

[0119] The following compounds b-10 and b-11 were used as antistatic agents in the comparative example: b-10: PEG Polyethylene glycol 4000 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. b-11: Sodium alkanesulfonate HOSTAPUR SAS93 manufactured by Clariant Japan Co., Ltd.

[0120] <Preparation of Resin Molded Products> An aqueous solution or aqueous dispersion of resin (a) was placed in a 200 mL beaker equipped with a magnetic stirrer. Antistatic agent (b) was added so that the mass ratio of (a):(b) was the predetermined mass ratio shown in Tables 1A, 1B, 1C, 2A, 2B, 3A, 3B, 4A, and 4B, and the mixture was stirred at room temperature for 15 minutes. The resulting solution was applied to a PTFE sheet or PET film processed to a size of 4 cm in length and 4 cm in width, and the water was evaporated to obtain a resin molded product.

[0121] <Evaluation of Resin Molded Products> The obtained resin molded products were left to stand overnight under conditions of 25°C and 40% RH, and the following evaluations were performed. [Appearance] The appearance of the resin molded products was visually evaluated according to the following criteria. ○: The resin molded product is transparent △: The resin molded product is slightly cloudy ×: The resin molded product is cloudy

[0122] [Surface Resistivity] The antistatic performance of the resin molded product was evaluated by measuring its surface resistivity. The surface resistivity was measured under conditions of 25°C, 40% RH environment, and an applied voltage of 100V using a HIOKI SM-8220 super-insulation meter and an SME-8311 electrode for flat plates.

[0123] The results of the visual evaluation and surface resistivity measurement are shown in Tables 1A, 1B, 1C, 2A, 2B, 3A, 3B, 4A, and 4B.

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] From the results described in Tables 1A, 1B, 1C, 2A, 2B, 3A, 3B, 4A, and 4B, it was confirmed that the resin molded articles of the examples to which the synthesized compounds b-1 to b-9 were added as antistatic agents exhibited excellent transparency and a decrease in surface resistivity. On the other hand, it was confirmed that the resin molded articles of the comparative examples to which no antistatic agent was added, or to which the antistatic agents b-10 and b-11 were added, exhibited poor transparency or did not decrease significantly in surface resistivity.

[0134] In Examples 1 to 15, where polyvinylpyrrolidone was used as resin (a), antistatic agents having a monohydroxyhydrocarbon group as the amine compound showed excellent antistatic performance, with those containing 2-aminoethanol showing the best results. Furthermore, in Examples 1, 4, 8, and 11, antistatic agents having phosphoric acid as the acid showed excellent antistatic performance.

[0135] In Examples 16 to 33, where polyacrylic acid was used as resin (a), antistatic agents having a polyhydroxy hydrocarbon group as the amine compound showed superior antistatic performance. Furthermore, in Examples 16, 19, 25, and 28, antistatic agents having a carboxylic acid as the acid showed superior antistatic performance.

[0136] In Examples 34 to 51, in which polyvinyl alcohol was used as resin (a), antistatic agents having phosphoric acid as the acid showed superior antistatic performance.

[0137] In Examples 52 to 69, where acrylic resin was used as resin (a), antistatic agents having phosphoric acid as the acid showed superior antistatic performance.

Claims

1. Containing (A) an amine compound and (B) an acid, wherein (A) the amine compound is represented by the following formula (I) or (II): (In the formula, R a each independently represents a linear or branched hydroxyhydrocarbon group having 1 to 22 carbon atoms and having one or more hydroxyl groups, R b each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and c represents an integer of 1 to 3.) (In the formula, R 1 represents a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, R 2 each independently represents a hydrogen atom or a monovalent or divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, R 3 represents a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, l represents 0 to 2, m represents 0 to 2, and n represents 0 or 1. R 1 and R 2 may together form a ring having 3 to 22 carbon atoms. X represents a hydrogen atom or a monovalent cation.) and (B) the acid is a phosphoric acid or a carboxylic acid, an antistatic agent.

2. (B) The antistatic agent according to claim 1, wherein the acid is a phosphinic acid, a phosphonic acid, or a phosphoric acid, and the carboxylic acid is a saturated aliphatic hydroxycarboxylic acid.

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