WO2008029760A1

WO2008029760A1 - Novel resin, method for producing the same, novel composition, and cured product obtained by curing the composition

Info

Publication number: WO2008029760A1
Application number: PCT/JP2007/067127
Authority: WO
Inventors: Hiroshi Uchida; Kazuhiko Ooga
Original assignee: Showa Denko K.K.
Priority date: 2006-09-06
Filing date: 2007-09-03
Publication date: 2008-03-13
Also published as: JPWO2008029760A1; TW200831561A; JP5546128B2

Abstract

Disclosed is a resin which is characterized by having a molecular chain wherein a plurality of organic groups represented by the formula (I) below are bound together, and having a weight average molecular weight of 10,000-300,000. (I) (In the formula, C represents a divalent organic group having a divalent hydrocarbon chain with 30-50 carbon atoms; and A represents an amide bond, an ester bond, a urethane bond, a urea bond or a carbonate bond.) This resin is able to exhibit flame retardancy of UL-94 VTM-0 grade without using a halogen-containing flame retardant or a phosphorus flame retardant, and enables to easily obtain a cured product having flame retardancy of UL-94 VTM-0 grade.

Description

Specification

Novel resin, process for producing the same, novel composition, and cured product obtained by curing the composition

Technical field

The present invention relates to a novel resin, a method for producing the same, a novel composition, and a cured product obtained by curing the composition. More specifically, the present invention relates to a novel resin that does not contain halogen or phosphorus and can exhibit VTM-0 flame retardancy in a flame retardancy test by UL94 V TM method, and the flame retardancy The present invention relates to a method for producing a resin. In addition, the present invention provides a novel composition capable of obtaining a cured product capable of exhibiting flame retardancy of VTM-0 in a flame retardancy test by UL94 VTM method, and flame retardancy formed by curing the composition. Relates to the cured product.

Background art

[0002] In recent years, electronic devices for communication, consumer use, industrial use, and the like have become stricter in required properties in terms of materials because of their higher density, higher functionality, and environmental aspects. For example, flexible printed wiring boards, their adhesives, coverlays, covercoats, etc. are required to have electrical properties such as flame retardancy, mechanical properties, chemical resistance, and migration resistance.

[0003] The adhesive comprising the resin composition used for the coverlay or covercoat has strong adhesion between the polyimide film or polyethylene terephthalate film and the copper foil, as well as repeated bending and displacement. It is required that the insulation properties of the wiring circuit made of the copper foil can be maintained, moisture and flaws from the outside can be prevented, and that the flame resistance should pass the UL standard. For this reason, the adhesive based on epoxy resin is appropriately combined with a flame retardant, a rogen-based flame retardant, a metal hydrate, a phosphorus compound, and the like to obtain flame retardancy.

[0004] In general, a flame retardant mechanism using a halogen-based flame retardant exhibits flame retardancy by trapping radicals in the gas phase generated during combustion. Although this flame retardant mechanism is versatile, halogen-based flame retardants generate toxic gas (hydrogen halide gas) during combustion, and there are environmental problems such as dioxin generated due to incomplete combustion during incineration. It has been pointed out.

[0005] Further, the flame retardant mechanism using metal hydrate is a force S that expresses flame retardancy by releasing water when the metal hydrate burns, and it is actually necessary to add a large amount. Therefore, there is a problem that the mechanical properties and adhesiveness are deteriorated.

[0006] Further, in the flame retardant mechanism using a phosphorus compound, the presence of the phosphorus compound forms a carbonized film called "chia" on the surface layer of the combustion product, and as a result, flame retardancy is exhibited. Thus, although it is preferable from the viewpoint of flame retardancy, it has been pointed out that there is a problem that the adhesion resistance is lowered and the migration resistance is lowered.

[0007] In view of this, Patent Document 1 and Patent Document 2 have proposed to improve the migration property when a phosphorus compound is used as a flame retardant. In other words, the addition of NBR rubber with low ionic impurities or the use of a phenolic curing agent as a curing agent for epoxy resin is intended to prevent a decrease in migration resistance.

[0008] Further, Patent Document 3 describes that the migration resistance is improved by adding a polyester resin to the adhesive composition.

Patent Document 1: JP 2001-339131 A

Patent Document 2: JP 2001-339132 A

Patent Document 3: JP 2001-31940 A

Disclosure of the invention

Problems to be solved by the invention

[0009] However, copper migration is caused by corrosion of copper due to moisture, chlorine ions in epoxy resin, ionic impurities in NBR, and the like. For this reason, as in Patent Document 1, in the case where a compound having a water absorption property such as a phosphorus compound and easily ionized is added, an NBR rubber with a small amount of ionic impurities is added to improve the migration resistance. Even if added, there was a limit.

[0010] Further, as in Patent Document 3, when an adhesive composition to which a polyester resin is added is used, there is a problem that heat resistance is lowered.

[0011] On the other hand, flame retardancy can be expressed with a new flame retardant mechanism different from the above flame retardant mechanism. In both cases, a resin and a composition capable of obtaining a cured product having excellent electrical insulation are desired.

[0012] Therefore, an object of the present invention is to solve the problems of the prior art. More specifically, the object of the present invention is to obtain a cured product that exhibits flame retardancy and is excellent in electrical insulation by a new flame retardant mechanism that is different from conventional flame retardant technologies such as the use of phosphorus compounds. It is to provide a novel flame retardant resin and a novel composition. Another object of the present invention is to provide a cured product excellent in flame retardancy and electrical insulation obtained by these novel flame retardant resins and novel compositions.

Means for solving the problem

[0013] As a result of intensive studies on the above problems, the present inventors have found that if a specific repeating unit is contained in a resin or a cured product, it becomes difficult to sustain combustion, and the present invention has been completed. It was.

[0014] That is, the present invention is summarized as follows.

[1] [1] It has a molecular chain in which a plurality of organic groups represented by the following formula (I) are bonded, and has a weight average molecular weight.

A special note of the moon that is 10,000-300,000.

[0016] [Chemical 1]

(In the formula, C is a divalent organic group having a divalent hydrocarbon chain having 30 to 50 carbon atoms, and Α is an amide bond, an ester bond, a urethane bond, a urea bond, or a carbonate bond. is there

[2] The C is a polyol having a hydrocarbon chain having 30 to 50 carbon atoms, a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms, or a poly having a hydrocarbon chain having 30 to 50 carbon atoms. The resin according to [1], which is derived from an acid anhydride, a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms, or a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms. .

[3] The resin according to [1] or [2] above, which is an organic group having the C force cyclohexane ring and / or cyclohexene ring.

[0020] [4] The above [;!, Which is accompanied by at least one reaction of the following ( _a ) to (j): ] ~ [3] The process for producing a resin as described in any of the above.

[0021] ( _a ) a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms or an ester of a lower alcohol of the polycarboxylic acid.

[0022] (b) A polycondensation reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

[0023] (c) A polyaddition reaction involving a decarboxylation reaction between a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

[0024] (d) A polyaddition reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms.

[0025] (e) A polyaddition reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms.

[0026] (f) Reaction of a polyol having a hydrocarbon chain having 30 to 50 carbon atoms with a dialkyl carbonate or diaryl carbonate, or a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and phosgene Polycarbonate formation reaction by reaction with.

[0027] (g) Polyurea production reaction by reaction of polyamine having a hydrocarbon chain having 30 to 50 carbon atoms with phosgene.

[0028] (h) A polycondensation reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms.

[0029] (i) A polyaddition reaction involving a decarboxylation reaction between a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms.

[0030] (j) An ester amide exchange reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid ester having a hydrocarbon chain having 30 to 50 carbon atoms.

[0031] [5] A composition comprising as essential components a resin as described in [1] to [3] above, and a curing agent having a functional group capable of reacting with the resin. And

The resin is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group and a primary or secondary amino group, and has reactivity with the curing agent. A resin consisting of molecules with m functional groups in one molecule, The curing agent is a curing agent composed of molecules having n functional groups capable of reacting with the resin in one molecule and having a hydrocarbon chain having 30 to 50 carbon atoms.

(The average value of m and n is 2 or more respectively, and the sum of the average value of m and the average value of n is 5 or more.)

[0032] [6] A hydrocarbon chain having 30 to 50 carbon atoms, a polyol having 3 or more hydroxyl groups in one molecule, and a hydrocarbon chain having 30 to 50 carbon atoms in one molecule Polycarboxylic acid having 3 or more carboxyl groups, polyanhydride having a hydrocarbon chain of 30 to 50 carbon atoms, hydrocarbon chain having 30 to 50 carbon atoms, and 3 or more isocyanates in one molecule A compound selected from the group consisting of a polyisocyanate having a group and a hydrocarbon chain having 30 to 50 carbon atoms, and having 3 or more primary or secondary amino groups in one molecule, And at least one compound whose functional group can react with the curing agent described below,

An essential component is at least one curing agent having two or more functional groups capable of reacting with the compound in a molecule and a hydrocarbon chain having 30 to 50 carbon atoms.

The composition characterized by the above-mentioned.

[0033] [7] The composition described in [5] or [6] above, further containing a phosphorus-containing organic compound.

[0034] [8] A cured product obtained by curing the composition according to [1] above, [5] to [7].

[0035] [9] The cured product according to [8], wherein the flame retardancy of VTM-0 is exhibited in a flame retardancy test by UL94 VTM method.

[0036] In this specification, any resin that is soluble in an organic solvent is defined as "resin" even if it is crosslinked. In addition, a product that has increased cross-linking density and as a result insolubilized in an organic solvent is defined as a “cured product”.

The invention's effect

[0037] According to the resin, composition and cured product of the present invention, the following advantages are obtained.

(1) The resin of the present invention can exhibit UL-94 VTM-0 level flame retardancy even when no halogen-containing flame retardant or phosphorus flame retardant is used. According to this resin, a cured product having flame retardancy of UL-94 VTM-0 level can be easily obtained.

(2) According to the composition of the present invention, a cured product having flame resistance of UL-94 VTM-0 level. Is easily obtained. UL-94 VTM—A relatively simple composition that does not require the addition of many ingredients in order to obtain a cured product having flame retardancy of 0 level.

(3) The cured product of the present invention exhibits UL-94 VTM-0 level flame retardancy and is excellent in electrical insulation.

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] The present invention will be specifically described below.

Examples of the compound used in the present invention include a polyol having a hydrocarbon chain having 30 to 50 carbon atoms, a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms, and a hydrocarbon chain having 30 to 50 carbon atoms. A polycarboxylic acid lower ester, a polyanhydride having a hydrocarbon chain having 30 to 50 carbon atoms, a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms, and a hydrocarbon chain having 30 to 50 carbon atoms. The polyamine which has is mentioned.

[0040] In the resin and cured product of the present invention obtained from these compounds, a plurality of carbon atoms of 30 to

50 divalent or higher-valent hydrocarbon chains are bonded through an amide bond, an ester bond, a urethane bond, a urea bond, or a carbonate bond. For this reason, the resin and the cured product of the present invention can exhibit excellent flame retardancy.

[0041] The reason why the resin and cured product of the present invention exhibit VTM-0 flame retardancy in the UL94 VTM flame retardancy test is not completely clear, but is due to the following mechanism. It is guessed.

[0042] In general, when a resin is heated by a flame, first, a portion of the molecular chain that is easily cleaved is cleaved. For example, carbon-carbon bonds of hydrocarbon chains are less likely to be cleaved than amide bonds, ester bond sites, carbonate bond sites, and urethane bond sites. Therefore, binding sites such as an amide bond, an ester bond site, a carbonate bond site, and a urethane bond site that are easily cleaved are first cleaved. Combustion generally takes place in the gas phase, so if the molecular chain becomes small (ie, the molecular weight of the molecule is small) due to the cleavage (decomposition reaction) and the molecular chain is low enough to be gasified, Force that will continue to burn in the gas phase If the molecular chain that has been decomposed exceeds a certain molecular weight, if the gas chain does not gasify, the combustion will continue at that point Does not generate flammable gas. So Therefore, the combustion action cannot be continued. In order to continue the combustion, the molecules having a certain molecular weight or more generated by thermal decomposition are further thermally decomposed to a molecular weight that can be gasified, and then burned in the gas phase. It is necessary to supply new heat energy and cause the next decomposition reaction.

On the other hand, since the decomposition reaction is an endothermic reaction, heat in the system can be absorbed. Therefore, if bonds that are easy to decompose break and molecular chains formed by decomposition do not gasify! / If the molecular chain can be stopped at such molecular weight, the endothermic heat generated by the decomposition reaction will increase the temperature in the system. As a result, combustion cannot be continued.

[0044] Like the resin and cured product of the present invention, the hydrocarbon structural unit has a carbon number in the range of 30 to 50, and the structural units are connected to each other through a bond that can be easily cleaved. In such a case, it is considered that the mechanism described above appears.

[0045] When the hydrocarbon structural unit has less than 29 carbon atoms, part or all of the molecular chain formed by decomposition tends to gasify and easily cause a combustion action. Further, when the hydrocarbon structural unit has 51 or more carbon atoms, the number of bond sites that are easily cleaved in the resin decreases, and as a result, the endothermic amount generated by the decomposition reaction becomes insufficient. It is difficult to suppress the temperature rise in the system.

[0046] In the compound used in the present invention, the hydrocarbon chain having 30 to 50 carbon atoms may have an epoxy ring.

[0047] Specific examples of the polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms include the following compounds (1) to (2).

[0048] [Chemical 2]

[0049] [Chemical 3]

(2)

[0050] Specific examples of the polyol having a hydrocarbon chain having 30 to 50 carbon atoms include the following compounds (3) to (5).

[0051] [Chemical 4]

[0052] [Chemical 5]

(Four)

[0053] [Chemical 6]

[0054] Specific examples of the polyamine having a hydrocarbon chain having 30 to 50 carbon atoms include the following compound (6).

[0055] [Chemical 7]

(CH ₂ ) ₇ CH ₂ NH ₂

[0056] Specific examples of the polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms include the following compound (7).

[0057] [Chemical 8]

The novel resin (A) of the present invention has a repeating unit represented by the following formula (I), and exhibits VTM-0 flame retardancy in a flame retardancy test by UL94 V TM method.

[0059] [Chemical 9]

[0060] In the formula (I), C is a divalent hydrocarbon chain having 30 to 50 carbon atoms as a main component. Each A is independently an amide bond, an ester bond, a urethane bond, a urea bond or a carbonate bond. In other words, the resin (A) has a molecular chain in which a plurality of organic groups represented by the above formula (I) are bonded. Resin (A) is, for example, C is a divalent hydrocarbon chain having 30 carbon atoms, and C is a divalent hydrocarbon chain having 35 carbon atoms next to the structural unit in which A is an amide bond. Multiple structural units may be bonded, such as a structural unit where A is an ester bond.

[0061] Here, A includes both —OCO— and —COO— in the case of an ester bond. Similarly, In the case of an amide bond, NHCO—CONH— and in the case of a urethane bond, both NHCO 2 O— and —OCONH— are included.

In the present specification, the “hydrocarbon chain” does not include carbon in the amide bond, ester bond, urethane bond, urea bond, and carbonate bond.

[0063] Further, it is desirable that 90% by mass or more of the total amount of carbon contained in all hydrocarbon chain units in one molecule is a divalent hydrocarbon chain having 30 to 50 carbon atoms. If the total amount of carbon contained in all hydrocarbon chain units in one molecule is a divalent hydrocarbon chain of 30 to 50% by mass, VTM— 0 in the flame resistance test of UL94 VTM method Whether to exhibit the flame retardancy of this depends on the structure of the resin and cannot be generally stated, but is preferably within the above range. From the viewpoint of flame retardancy, all of C is a divalent hydrocarbon chain having 30 to 50 carbon atoms (that is, a divalent organic group having a divalent hydrocarbon chain having 30 to 50 carbon atoms). I like it.

[0064] As the divalent hydrocarbon chain having 30 to 50 carbon atoms, dimer acid or hydrogenated dimer acid, and polyols, polyamines, and polyisocyanates derived from these compounds are preferable from the viewpoint of availability.

[0065] A is preferably a urethane bond or a carbonate bond from the viewpoint of easy development of flame retardancy and solubility in an organic solvent.

[0066] Further, the divalent hydrocarbon chain having 30 to 50 carbon atoms may have an epoxy ring which may have a substituent such as a hydroxyl group.

[0067] C is a polyol having a hydrocarbon chain having 30 to 50 carbon atoms, a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms, or a polyanhydride having a hydrocarbon chain having 30 to 50 carbon atoms. It is preferably derived from a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms or a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms. This is due to the ease of synthesis and the degree of freedom in molecular design. Further, C is preferably an organic group having a cyclohexane ring and / or a cyclohexene ring.

[0068] Specific examples of the repeating unit represented by the formula (I) include the following repeating units (8) to (8)

(19).

[0069] [Chemical 10]

[0070] [Chemical 11]

[0071] [Chemical 12]

[0072] [Chemical 13]

[0073] [Chemical 14]

[0074] [Chemical 15]

[0076] [Chemical 17]

[0077] [Chemical 18]

[0078] [Chemical 19]

[0081] Since the resin (A) has a repeating unit as described above, it is excellent in flame retardancy even when a halogen-containing flame retardant and a phosphorus flame retardant are not used. In other words, the flame retardancy test of UL94 VTM shows the flame retardancy of VTM-0 without using phosphorus flame retardant. The flame retardancy test method will be described in detail in the examples.

[0082] The (A) has a number average molecular weight of preferably 3,000-40,000, more preferably 4,000 0-30,000. The weight average molecular weight power is preferably 10,000 to 300,000, more preferably 15,000 to 100,000. [0083] The weight average molecular weight of the resin (A) is not particularly limited, but in general, when it is necessary to reduce the tack of the resin, the weight average molecular weight is 10,000 or more. It is preferable.

[0084] The weight average molecular weight described in the present specification is a value calculated from a calibration curve prepared using a polystyrene standard substance by gel permeation chromatography (hereinafter referred to as GPC). is there.

Next, a method for producing the resin (A) will be described.

[0086] The method for producing the resin (A) of the present invention is characterized by using at least one of the following reactions (a) to (a).

[Reaction (a)]

Reaction (a) is a polycondensation reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms or an ester of a lower alcohol of the polycarboxylic acid ( Esterification or transesterification reaction).

[0088] For example, a polycondensation reaction between the dicarboxylic acid represented by the formula (1) and / or the formula (2) and the diol represented by the formula (3) and / or the formula (4) is performed. Can be mentioned. In some cases, the polyol represented by the formula (5) may be used in combination with a diol within a range that does not gel.

[0089] The esterification reaction (polycondensation reaction) is a method generally used in the production of polyethylene terephthalate, or the solvent is refluxed in the presence of an acid catalyst in an organic solvent such as benzene or toluene. You may carry out by distilling off the water to produce | generate.

[0090] [Reaction (b)]

Reaction (b) is a polycondensation reaction (amidation reaction) between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

[0091] For example, a polycondensation reaction between the dicarboxylic acid represented by the formula (1) and / or the formula (2) and the diamine represented by the formula (6) can be exemplified.

[0092] The amidation reaction (polycondensation reaction) is carried out in a low-temperature organic solvent by using a method used when producing 6, 6-nylon or a condensing agent such as dicyclohexyl carpositimide. You may go. [0093] [Reaction (c)]

Reaction (c) is a polyaddition reaction involving decarboxylation of a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

Yes

[0094] For example, an amidation reaction involving a decarboxylation reaction between the dicarboxylic acid represented by the formula (1) and / or the formula (2) and the didiisocyanate represented by the formula (7) is performed. Can mention

[0095] This amidation reaction involving decarboxylation is generally carried out by heating using a catalyst such as dibutyltin dilaurate or tertiary amine. If necessary, the reaction may be carried out after diluting with an organic solvent! /.

[0096] [Reaction (d)]

Reaction (d) is a polyaddition reaction of a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms.

For example, a polyaddition reaction between the diisocyanate represented by the formula (7) and the diol represented by the formula (3) and / or the formula (4) can be mentioned. In some cases, the polyol represented by the above formula (5) can be used in combination with a diol as long as the gel is not gelled.

[0098] This polyaddition reaction is generally carried out by heating using a catalyst such as dibutyltin dilaurate, tertiary amine or carboxylic acid. If necessary, it may be diluted with an organic solvent to react fi.

[0099] [Reaction (e)]

Reaction (e) is a polyaddition reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms.

[0100] For example, a polyaddition reaction of the diisocyanate represented by the formula (7) and the diamine represented by the formula (6) can be mentioned.

[0101] This polyaddition reaction is generally carried out at room temperature or with heating in the absence of a catalyst. Also

If necessary, the reaction may be carried out by diluting with an organic solvent.

[0102] [Reaction (f)] Reaction (f) is a reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a dialkyl carbonate or diaryl carbonate, or a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and phosgene. It is a polycarbonate production | generation reaction by reaction of these.

[0103] First, the reaction of a polyol having a hydrocarbon chain having 30 to 50 carbon atoms with a dialkyl carbonate or diaryl carbonate is represented by, for example, the above (3) and / or (4) Examples include transesterification of diols with dialkyl carbonates such as dimethyl carbonate, jetyl carbonate, di-η-butylene carbonate or diaryl carbonates such as diphenyl carbonate.

[0104] In general, this polycarbonate-forming reaction is heated in the presence of a catalyst such as lead dioxide, tetraisopropoxytitan, or potassium carbonate to remove the generated alcohol or phenol out of the system. While done.

[0105] Further, the reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and phosgene is, for example, by reacting the diol represented by (3) and / or (4) with phosgene, This is done while removing the hydrochloric acid produced.

[0106] [Reaction (g)]

Reaction) is a polyurea formation reaction by the reaction of a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms with phosgene.

[0107] For example, the reaction is carried out while reacting diamine represented by the above formula)) with phosgene to remove the generated hydrochloric acid.

[Reaction (h)]

Reaction (h) is a polyamidation reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms.

[0109] For example, the diamine represented by the formula (6) and the polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms are reacted at room temperature or with heating.

[0110] [Reaction (i)]

Reaction (i) is a polyaddition reaction involving decarboxylation of a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms. It is. [0111] For example, the diisocyanate represented by the formula (7) and a polycarboxylic anhydride having a hydrocarbon chain having 30 to 50 carbon atoms are reacted by heating in the absence of a catalyst or in the presence of a catalyst.

Yes

[0112] [Reaction]

Reaction (j) is an ester amide exchange reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid ester having a hydrocarbon chain having 30 to 50 carbon atoms.

[0113] For example, a dicarboxylic acid ester is produced by an esterification reaction of the dicarboxylic acid represented by the formula (1) and / or the formula (2) with an alcohol such as allylic alcohol. This dicarboxylic acid ester and the diamine represented by the formula (6) are reacted by heating in the absence of a catalyst or in the presence of a catalyst. A polyamide compound can be obtained by distilling off the alcohol to the outside of the reaction system.

[0114] Among these, the preferred resin (A) and the production method thereof will be described in more detail below. .

[0115] (1) C has a structural unit derived from a diol having a hydrocarbon chain having 30 to 50 carbon atoms and a structural unit derived from a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms. As A, a resin (A) having a urethane bond is preferable from the viewpoint of easy development of flame retardancy and solubility in an organic solvent. In addition, 45 to 55 mol% of structural units derived from diol force and 45 to 55 structural units derived from diisocyanate based on the sum of structural units derived from diol force and structural units derived from diisocyanate. it is preferred to have mole ^_0/0.

[0116] This resin is obtained by a polyaddition reaction of a diol having a hydrocarbon chain having 30 to 50 carbon atoms and a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms (reaction (d)). Here, it is preferable to use 80 to 130 parts by mass of diisocyanate with respect to 100 parts by mass of the diol.

[0117] (2) C has a structural unit derived from a diol having a hydrocarbon chain having 30 to 50 carbon atoms and a structural unit derived from a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms. The resin (A) having a carbonate bond and a urethane bond as A is preferable from the viewpoint of easy development of flame retardancy and solubility in an organic solvent. Also, And pair the sum of the derived structural unit from structural units and Jiisoshianeto derived from Honoré, 60-80 mol of structural units diol force is also induced ^_0/0, the structural units derived from Jiisoshianeto 20-40 It is preferable to have mol%. It is preferable to have a carbonate bond of 60 to 80 mol% and a urethane bond of 20 to 40 mol% based on the total of the carbonate bond and the urethane bond! /.

[0118] This resin is obtained as follows. First, by using a diol having a hydrocarbon chain having 30 to 50 carbon atoms and dialkyl carbonate or diaryl carbonate, a polycarbonate having hydroxyl groups at both ends is produced (reaction (f)). Here, the amount of dialkyl carbonate or dialyl carbonate relative to 100 parts by weight of diol varies depending on the type of dialkyl carbonate or dialyl carbonate S, for example, when dimethyl carbonate is used, Generally, it is 1.5 to 4 parts by mass with respect to parts. Further, the jetyl carbonate may be added to the reaction vessel before the reaction all at once, or may be intermittently added as the reaction proceeds.

Next, a resin (A) is obtained by a polyaddition reaction between the obtained polycarbonate and a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms (reaction (d)). Here, it is preferable to use 17 to 55 parts by mass of diisocyanate with respect to 100 parts by mass of polycarbonate.

[0120] (3) A structural unit derived from a diol having a hydrocarbon chain having 30 to 50 carbon atoms as C, a structural unit derived from a dicarboxylic acid power having a hydrocarbon chain having 30 to 50 carbon atoms, and the number of carbon atoms A resin (A) having a structural unit derived from a diisocyanate having 30 to 50 hydrocarbon chains and having an ester bond and a urethane bond as A is preferable from the viewpoint of solubility in an organic solvent. In addition, 50 to 70 mol% of structural units derived from diol and 50% to 70 mol% of structural units derived from diol with respect to the total of structural units derived from diol power, structural units derived from dicarboxylic acid power, and structural units derived from diisocyanate. It is preferred to have 15 to 35 mol% of derived structural units and 15 to 35 mol% of structural units derived from diisocyanate! /. It is preferable to have 30 to 70 mol% of ester bonds and 30 to 70 mol% of urethane bonds with respect to the total of ester bonds and urethane bonds.

[0121] This resin is obtained as follows. First, it has a hydrocarbon chain with 30 to 50 carbon atoms A polyester diol having hydroxyl groups at both ends is produced by a polycondensation reaction of the diol with a dicarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms (reaction (a)). Here, it is preferable to use 50 to 85 parts by mass of the dicarboxylic acid with respect to 100 parts by mass of the diol.

[0122] Next, a resin (によって) is obtained by a polyaddition reaction of the obtained polyester diol with a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms (reaction (d)). Here, it is preferable to use 17 to 55 parts by mass of diisocyanate with respect to 100 parts by mass of polyester diol.

[0123] (4) As C, a structural unit derived from a diol having a hydrocarbon chain having 30 to 50 carbon atoms, a structural unit derived from diamine having a hydrocarbon chain having 30 to 50 carbon atoms, and carbon A resin having a structural unit derived from a diisocyanate having a hydrocarbon chain of several 30 to 50, and having a urethane bond obtained from diol and diisocyanate and a urea bond obtained from diamine and diisocyanate as A (A ) Is preferable from the viewpoint of flame retardancy. Further, the structural unit, relative to the total amount of the structural units derived from the structural units of and Jiisoshianeto derived Jiamin force, 15 to 35 mol of structural units induction diol ^_0/0 derived from a diol, Jiamin It is preferable to have 15 to 35 mol% of structural units derived from bismuth and 50 to 70 mol% of structural units derived from diisocyanate. The total of the urethane bond and Urea bond, 50 to 70 mol% of the urethane bond, the Urea bond preferably has 30 to 50 mole ^_0/0.

[0124] This resin is prepared by mixing a diol having a hydrocarbon chain having 30 to 50 carbon atoms, a diamine having a hydrocarbon chain having 30 to 50 carbon atoms, and a diisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms. The polyaddition reactions (d) and (e) can be performed simultaneously. Here, it is preferable to use 40 to 40 mass parts of diamine and 140 to 470 mass parts of diisocyanate with respect to 100 mass parts of diol! /.

[0125] (5) As C, a structural unit derived from a dicarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms and a structural unit derived from diamine having a hydrocarbon chain having 30 to 50 carbon atoms And A as the resin (A) having an amide bond is preferable from the viewpoint of high ability to form a self-supporting film. It is also derived from structural units derived from dicarboxylic acid power and diamine. The total of the electrically the structural units, the structural units derived from dicarboxylic acids 45-55 mole ^_0/0, it is preferred to have from 45 to 55 mol% of structural units derived from Jiamin.

[0126] This resin is obtained as follows. First, a dicarboxylic acid ester is produced by an esterification reaction between a dicarboxylic acid having a hydrocarbon chain of 30 to 50 carbon atoms and an alcohol such as allylic alcohol. Here, it is preferable to use 2.;! To 3 moles of alcohol with respect to 1.0 mole of dicarboxylic acid.

Next, the dicarboxylic acid ester is reacted with diamine having a hydrocarbon chain having 30 to 50 carbon atoms to obtain a resin (A) (reaction). Here, it is preferable to use 1.005-1.3 mol of diamine with respect to 1.0 mol of dicarboxylic acid ester.

[0128] <Composition (B)>

The composition (B) of the present invention is a composition comprising the above-described resin and a curing agent having a functional group capable of reacting with the resin as essential components,

The resin is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group and a primary or secondary amino group, and has reactivity with the curing agent. A resin composed of molecules having m functional groups in one molecule, and the curing agent has n functional groups capable of reacting with the resin in one molecule, and is carbonized with 30 to 50 carbon atoms. It is a curing agent consisting of molecules with hydrogen chains

[0129] That is, the composition (B) of the present invention contains a resin (硬化 ') and a curing agent (E). The resin (Α ′) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, and a primary or secondary amino group in the resin (Α) described above. It is a resin composed of molecules having m functional groups in one molecule that can react with the functional groups of the curing agent (Ε).

[0130] The curing agent (E) is a curing composed of molecules having n functional groups capable of reacting with the functional group of the resin (Α ') per molecule and having a hydrocarbon chain of 30 to 50 carbon atoms. It is an agent. It is preferably selected from the compounds used in the present invention described above.

[0131] The average value of m and n is 2 or more respectively, and the sum of the average value of m and the average value of n is 5 or more It is. The reason is that when the average value of m and the average value of n are less than the sum, it is impossible to have a three-dimensional bridge structure. In addition, each m of the molecules forming the resin (Α ′) is preferably an integer of 2 to 8, more preferably 2 to 6, and each n of the molecules forming the curing agent (E) is , Preferably an integer of 2-8, more preferably 2-6. The average value of m is preferably 2 to 8, more preferably 2 to 6. The average value of n is preferably 2 to 8, more preferably 2 to 6.

[0132] Further, the sum of the average value of m and the average value of n is preferably in the range of 5 to 12; more preferably 6

~; In the range of 10.

[0133] The average value of m and the average value of n are defined as follows.

[0134] m is calculated from the number of functional groups of the raw material of the resin (Α '). For example, when the diol and the triisocyanate compound are reacted at a molar ratio of 4: 5, the resin (Α' ) The average number of functional groups (isocyanate groups) present in one molecule is 3 X 5-2 X 4 = 7, that is, the average length of m is 7.

[0135] The curing agent (E) may be a single molecular weight compound or a compound having a molecular weight distribution. The curing agent (E) is a single molecular weight compound having four hydroxyl groups. As can be seen from the structural formula, n = 4. In this case, the average value of n is also 4 as it is. In the case of a molecular weight distribution, for example, in the case of a curing agent (E) obtained by reacting a diisocyanate compound and triol in a molar ratio of 4: 5, the average functional group present in one molecule of the curing agent (E). The number of (hydroxyl groups) is 3 × 5−2 × 4 = 7, that is, the average value of n is 7.

[0136] The composition (B) has a force that makes it difficult to roughly define the compounding ratio by the combination of the resin (Α ') and the curing agent (Ε). For example, the curing agent (Ε) contains phosphorus. When the curing agent itself has a structure that can contribute to the flame retardant performance, such as a compound having a hydrocarbon chain of 30 to 50 carbon atoms, the mass ratio of the resin (Α ′) and the curing agent (Ε) is This is not a problem, and only the ratio of the number of functional groups contained in the resin (Α ') and the curing agent (Ε) has a significant effect. That is, the composition (Β) preferably has a ratio of the number of functional groups of the resin (Α ′) to the number of functional groups of the curing agent (Ε) in the range of 0.6 to 65-2, more preferably 0.8 to ; It is desirable to be in the range of 1.5.

[0137] When the curing agent (Ε) is a compound that does not have a structure that can contribute to flame retardancy, the mass ratio of the resin (Α ') to the curing agent (Ε) It becomes important in expression. That is, It is preferably 10 parts by mass or less and more preferably 7 parts by mass or less with respect to 100 parts by mass of the resin (Α ′). Further, as described above, it is preferable to set the ratio of the functional group number of the resin (Α ′) to the functional group number of the curing agent (Ε) within the range of 0.65 to 2, more preferably 0.8 to; 1. The range of 5 is desirable.

The resin (Α ′), which is an essential component of the composition (Β), is, for example, a reaction product of a polyhydric alcohol represented by the structural formula 5 and a diisocyanate represented by the structural formula 7. Resin composed of molecules having 4 or more hydroxyl groups in one molecule (Α'-1), diisocyanate represented by the structural formula 7 and diamine of the structural formula 6, wherein the number of isocyanate groups is larger than the number of amines. It is possible to cite the reaction product obtained by reacting with (1) or (2) a resin having two isocyanate groups in one molecule. In this case, in the resin (Α′-1), the average value of m is preferably 4 to 8. In the resin (樹脂 '-2), the average value of m is 2.

[0139] Further, as the curing agent (E), which is an essential component of the composition (B), for example, when the resin (Α'-1) is used as the resin ('), the structural formula The diisocyanate represented by 7 can be mentioned. In this case, the average value of η is 2, and a urethane bond is generated by the reaction between the functional groups of the resin (Α′-1) and the curing agent (Ε), and a cured product is obtained by crosslinking. Further, when the resin (Α′-2) is used as the resin (Α ′), for example, an government capable of reacting with an isocyanate group in one molecule such as a polyol represented by the structural formula 5 above. Examples thereof include compounds having a functional group. In this case, the average value of η is 4, and a urethane bond is formed by the reaction between the functional groups of the resin (Α′-2) and the curing agent (Ε), and a cured product is obtained by crosslinking.

[0140] <Composition (C)>

The composition (C) of the present invention has a hydrocarbon chain having 30 to 50 carbon atoms, a polyol having 3 or more hydroxyl groups in one molecule, a hydrocarbon chain having 30 to 50 carbon atoms, A polycarboxylic acid having 3 or more carboxyl groups in the molecule, a polyanhydride having a hydrocarbon chain having 30 to 50 carbon atoms, a hydrocarbon chain having 30 to 50 carbon atoms, and 3 in one molecule Selected from the group of polyisocyanates having at least one isocyanate group and polyamines having a hydrocarbon chain of 30 to 50 carbon atoms and having at least 3 primary or secondary amino groups in one molecule At least one compound which is a compound and whose functional group can react with the curing agent described below. Seeds,

It is characterized by that.

[0141] That is, the composition (C) of the present invention contains at least one compound (F) and a curing agent (G). Compound (F) has a hydrocarbon chain having 30 to 50 carbon atoms, a polyol having 3 or more hydroxyl groups in one molecule, a hydrocarbon chain having 30 to 50 carbon atoms, and one molecule A polycarboxylic acid having 3 or more carboxyl groups, a polyanhydride having a hydrocarbon chain having 30 to 50 carbon atoms, a hydrocarbon chain having 30 to 50 carbon atoms, and 3 or more in one molecule A compound selected from the group of polyisocyanates having an isocyanate group and polyamines having a hydrocarbon chain of 30 to 50 carbon atoms and having three or more primary or secondary amino groups in one molecule. Thus, the functional group of this compound can react with the functional group of the curing agent (G). The curing agent (G) has at least one functional group capable of reacting with the functional group of the compound (F) in one molecule, and has at least one kind of hydrocarbon chain having 30 to 50 carbon atoms. It is a curing agent. The compound (F) and the curing agent (G) are preferably selected from the compounds used in the present invention described above.

[0142] The composition (C) has a force that makes it difficult to generally define the compounding ratio by the combination of the compound (F) and the curing agent (G). For example, the curing agent (G) contains phosphorus. When the curing agent itself, such as a compound or a compound having a hydrocarbon chain having 30 to 50 carbon atoms, has a structure that can contribute to flame retardancy, the mass ratio of the compound (F) and the curing agent (G) is not so much. This is not a problem, and only the ratio of the number of functional groups contained in the compound (F) and the curing agent (G) has a great influence. That is, the composition (C) preferably has a ratio of the number of functional groups of the compound (F) to the number of functional groups of the curing agent (G) in the range of 0.65 to 2, more preferably 0.8 to; 1. Desirable to be in the range of 5

Yes

[0143] In addition, when the curing agent (G) is a compound that does not have a structure that can contribute to flame retardancy, the mass ratio of the compound (F) and the curing agent (G) increases the flame retardancy. It becomes important in. That is, it is preferably 10 parts by mass or less and more preferably 7 parts by mass or less with respect to 100 parts by mass of the compound (F). As described above, the functional number of the compound (F) and the curing agent (G) The ratio of the number of functional groups is preferably in the range of 0.65 to 2, more preferably in the range of 0.8 to 1.5.

[0144] As an example of the compound (F), which is an essential component of the composition (C), when the compound represented by the structural formula 5 is used, as the curing agent (G), for example, The compound represented by the structural formula 1, the compound represented by the structural formula 2, the compound represented by the structural formula 7, and the like can be exemplified. When the compound represented by the structural formula 5 is combined with the compound represented by the structural formula 1 or the compound represented by the structural formula 2, the compound (F) and the curing agent (G) An ester bond is formed by the reaction between the functional groups, and a cured product is obtained by crosslinking. When the compound represented by the structural formula 5 and the compound represented by the structural formula 7 are combined, a urethane bond is formed by the reaction between the functional groups of the compound (F) and the curing agent (G). Generated and cross-linked to obtain a cured product.

[0145] The composition (i) or the composition (C) of the present invention has excellent flame retardancy and electrical insulation even when it does not contain a phosphorus-containing organic compound. It may contain a contained organic compound.

[0146] The phosphorus-containing organic compound used in the present invention is not particularly limited as long as it is an organic compound that exhibits flame retardancy and contains phosphorus in the molecule.

[0147] Examples of the phosphorus-containing organic compound include the following compounds.

[0148] [Chemical 22]

[0149] [Chemical 23]

[0150] [Chemical 24]

[0151] [Chemical 25]

[0152] [Chemical 26]

[0153] [Chemical 27] General formula (1)

[0154] (General formula (1)

R ² is a monovalent linear or branched alkyl group having 1 to 6 carbon atoms or aryl groups which may be the same or different from each other, and M is Mg, Ca, A 1, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, U, Na, K force, metal selected from at least one of the group consisting of m, It is an integer of 4. )

[0155] [Chemical 28]

2-

0 0

0- ■

n General formula (2)

(R ⁴ and R ⁵ in the general formula (2) are a monovalent linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group which may be the same or different from each other. R ³ is a divalent linear or branched carbon number;! To 10 alkylene group, or 6 to 6 carbon atom; arylene group, alkylarylene group or arylene alkylene group. Yes, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K force, at least one of the group And n is an integer from;! To 4 and X is an integer from;! To 4.)

Also, for example, the following phosphorus-containing epoxy group-containing compounds and the following phosphorus-containing alcohol-containing organic compounds such as phosphorus-containing alcohols can be used.

[0157] [Chemical 29]

[0158] [Chemical 30]

No 3

[0159] Among these phosphorus-containing organic compounds, those that do not deteriorate the heat resistance in the composition are preferred. Specifically, the phosphinic acid salt represented by the general formula (1) or the general formula (2) There are diphosphinates and reactive phosphorus-containing organic compounds. Examples of the phosphinate represented by the general formula (1) or the diphosphinate represented by the general formula (2) include OP-930 (trade name) or OP-935 manufactured by Clariant Japan Co., Ltd. It hits it. Examples of the reactive phosphorus-containing organic compound include the phosphorus-containing epoxy group-containing compound and the phosphorus-containing alcohol.

[0160] The mixing ratio of the phosphorus-containing organic compound in the composition (B) or (C) of the present invention is in the range of 5 to 50% by mass relative to the total amount of the composition (B) or (C). From the balance of film strength and flame retardancy, it is preferable.

[0161] The composition (B) or (C) of the present invention may further contain a catalyst in order to accelerate the curing reaction for producing the cured product (E) of the present invention described later. The catalyst has different forces depending on the reaction mode of the curing reaction. For example, when a curing reaction is performed by a reaction between a hydroxyl group and an isocyanate group, an organic tin compound such as dibutyltin dilaurate, or 2, 4, 6-tris (N , N-dimethylaminomethyl) phenol can be used as a catalyst. In addition, when the curing reaction is an addition reaction between an epoxy group and a carboxylic acid, for example, melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyllochetyl S-triazine, 2,4-methacryloyloxychee. Chiru s—Triazine, 2, 4—Diamino 1—Bulu 1 s—Triadine, 2, 4—Diamino 6—Bulu 1 s—Tria Compounds having a triazine ring, such as gin'isocyanuric acid adduct, imidazole, 2-methinoreidamidazolene, 2-ethyl 4-methylimidazole, 2-phenylimidazonole, 2-undecylimidazole, 2-heptadecylimidazole 1 Benzylue 2—Methyl imidazole, 2 Phenyl leu 4-Methylimidazole, 1-Cyanethyl 2 Methyl imidazole, 1-Cyan Etinore 2 Ethinore 4-Metinoreidamidole, 1 Aminoethinore , 1 aminoethyl-2 methylimidazole, 1 (cyanethinoreaminoethinole) 2-methinoreidamidole, N— [2- (2-methinoreyl 1 imidazolyl) ethyl] urea, 1-cianoethyl-2-undecylimidazole 1-sianoethyl 2-methylimidazo 1-cyanethyl 1-cyanethyl 1-cyanethyl trimellitate, 1-cyanethyl 2-methyl 4-methyl imidazolium trimetrate 1-cyanethyl 2-undecyl imidazolium trimellitate 2, 4, 6— [2,1-Methylimidazolyl 1 (1,)] — Ethyl s triazine, 2, 4—Diamino 1 6— [2, Undecyl imidazolyl (1,)] ethyl s—Triazine, 2, 4 Diamino 1-6- [2, 1-ethyl-1 4'-methylimidazolyl (1,)] 1-ethyltris, 1- 1 dodecyl-2-methyl-3 3-benzylimidazolium chloride, N, N, 1bis (2 methyl) 1 imidazolylethyl) urea, N, N 'bis (2-methyl-1 imidazolylethyl) adipamide, 2 phenyl 4-methyl-5 hydroxymethylimi Dazole, 2 phenolinore 4.5 dihydroxymethylimidazole, 2 methylimidazole 'isocyanuric acid adduct, 2 phenylimidazole' isocyanuric acid adduct, 2, 4 diamino-6— [2'-methylimidazolyl (1 ')] -Etilru s-triazine' isocyanuric acid adduct, 2-methyl-4-phenoloremino imidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methylformylimidazole, 1-benzenore 2 Phenylimidazole, 1,2-Dimethylimidazole, 1- (2-Hydroxyethyl) imidazo monole, Burimidazole, 1-Methylimidazole, 1-Alilimidazole, 2-Ethenoreidamidole, 2 Butylimidazole, 2-Butyl-5-hydroxymethylimidazole, 2, 3-di Dro 1H-pyro-mouth [1, 2, a] benzimidazole, 1-benzyl 1-phenylene hydrazol hydrobromide, 1-dodecyl-2 methyl-3-benzimidazole and its derivatives, dicyandiazide, trif Enilphos A catalyst such as a fin can be used.

[0162] The amount of these catalysts used varies depending on the type of catalyst and the type of curing, but when a catalyst is used, the total amount of composition (B) in composition (B) is 100 masses in composition (B). The amount is preferably 0.1 part by mass to 5 parts by mass with respect to the part. In composition (C), it is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of composition (C) whole quantity.

[0163] The compositions (B) and (C) of the present invention may further contain an antifoaming agent in order to improve workability. The antifoaming agent is literally not particularly limited as long as it has an action of eliminating bubbles generated when the compositions (B) and (C) of the present invention are printed.

[0164] Specific examples of the antifoaming agent include, for example, BYK-077 (manufactured by Big Chemie Japan), SN deformer 470 (manufactured by San Nopco), TSA750S (manufactured by GE Toshiba Silicone), silicone Silicone defoaming agent such as Oil SH-203 (Toray Silicone), Dappo SN-348 (San Nopco), Dappo SN-354 (San Nopco), Dappo SN- Acrylic polymer antifoaming agents such as 368 (manufactured by Sannopco), acetylene such as Surfynol DF 110D (manufactured by Nisshin Chemical Industry), Surfynol DF—37 (manufactured by Nisshin Chemical Industry) Examples include diol-based antifoaming agents, fluorine-containing silicone-based antifoaming agents such as FA-630.

Of these, preferred antifoaming agents are silicone antifoaming agents and fluorine-containing silicone antifoaming agents, and more preferred are silicone antifoaming agents.

[0166] The amount of the antifoaming agent used in the composition (B) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the composition (B). In composition (C), it is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of composition (C) whole quantity.

[0167] In addition, the compositions (B) and (C) of the present invention may be used, if necessary, for example, ketones such as methylethylketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and methanol. , Alcohols such as isopropanol and cyclohexanol, cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, petroleum solvents such as petroleum ether and petroleum naphtha, cellosolves such as ethyl sucrose solve and butyl sucrose solve, Carbitols such as ethyl carbitol and butyl carbitol, ethers such as dimethoxyethane and diethoxyethane, ethyl acetate, butyl acetate, methoxyethyl acetate, propylene group Acetic esters such as recall monomethyl ether acetate, ethyl acetate sorb acetate, butyl cello soleb acetate, diethylene glycol eno methino oleate acetate, diethylene glycol mono butyl ether acetate, cyclic esters such as γ-butyl rataton, Ν-methylpyrrolidone, Known solvents such as amide solvents such as Ν and ジメチル -dimethylacetamide may be contained. These solvents may be used alone or in combination of two or more solvents.

[0168] The amount of these solvents used depends on each component of the composition and cannot be generally stated. However, when it is necessary to use a solvent, the total amount of the composition (Β) is 100%. In composition (C), which is preferably 10 parts by mass to 60 parts by mass with respect to parts by mass, it is 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total amount of composition (C). It is preferable.

[0169] Further, the compositions (Β) and (C) of the present invention may contain, as necessary, phthalocyanine blue, phthalocyanine 'green, eye gin' green, diso yellow, crystal violet, titanium oxide, carbon black, It may contain a known colorant such as naphthalene black.

[0170] When these colorants are used, the amount of the colorant used in the composition (Β) is 100 parts by mass when the mass of the organic solvent is removed from the total mass of the composition (Β). 0 to; 3.0 to 3.0 parts by mass is preferable. In the composition (C), when the mass excluding the mass of the organic solvent from the total mass of the composition (C) is 100 parts by mass, it is preferably 0.;! To 3.0 parts by mass

Yes

[0171] Furthermore, the compositions (C) and (C) of the present invention may contain an inorganic compound such as silica, if necessary.

[0172] In the case of using these inorganic compounds, the amount used is in the case of the composition (Β) when the mass obtained by subtracting the mass of the organic solvent from the total mass of the composition (Β) is 100 parts by mass. 0.1 mass part to 30 mass parts is preferred!

[0173] In general, the compositions (i) and (C) of the present invention can be obtained by uniformly kneading and mixing a part or all of the compounding components by a kneading mill, a bead mill or the like.

[0174] <Hardened product (D)>

The cured product (D) of the present invention is obtained by curing one or more of the compositions (B) and (C) of the present invention. The As described above, the cured product (D) does not require the addition of many components and can be easily obtained by a composition having a relatively simple composition.

[0175] The curing conditions for obtaining the cured product (D) differ depending on the curing type. For example, when the curing reaction is performed by the reaction of a hydroxyl group and an isocyanate group, the curing can be performed by heating without using a catalyst, It is hardened by heating at room temperature or by using an organotin compound such as dibutyltin dilaurate or a tertiary amine such as 2,4,6-tris (N, N-dimethylaminomethyl) phenol as a catalyst. You can be tricked.

[0176] The cured product (D) thus obtained is bonded through a plurality of divalent hydrocarbon chains having 30 to 50 carbon atoms, amide bonds, ester bonds, urethane bonds, urea bonds, or carbonate bonds. is doing. That is, the cured product (D) is formed by crosslinking the structure of the formula (I). Therefore, the cured product (D) of the present invention can exhibit UL-94 VTM-0 level flame retardancy even when no halogen-containing flame retardant or phosphorus flame retardant is used. The flame retardancy test method will be described in detail in the examples.

[0177] Further, the cured product (D) is excellent in electrical insulation!

[0178] [Example]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[0179] <Measurement of average molecular weight>

The GPC measurement conditions are as follows.

[0180] Instrument name: HPLC unit HSS-2000 manufactured by JASCO Corporation

Column: Shodex column: LF—804

Mobile phase: tetrahydrofuran

Flow rate: 1. OmL / min

Detector: manufactured by JASCO Corporation RI— 2031 P1US

Temperature: 40. 0 ° C

Sample volume: 100 liters of sample loop

Sample concentration: 0.1 Prepared at around 1% by mass

Under the above measurement conditions, using a calibration curve created using polystyrene standards The weight average molecular weight was calculated.

[0181] [Example 1]

In a reaction vessel equipped with a stirrer, thermometer and condenser, hydrogenated dimer diol (trade name: SOVERMOL908 COGNIS hydrocarbon number 36 carbon atoms) 53. 71 g as polymer polyol and dimer isocyanate as diisocyanate compound Compound (trade name: DDI1410 manufactured by COGNIS) 60. 1 lg and propylene glycol monomethyl ether acetate (produced by Daicel Chemical Co., Ltd.) 115.4 g as a solvent were charged at 100 ° C for 3 hours and at 110 ° C for 3 hours. After 3 hours of reaction at 120 ° C for 3 hours and confirming that the isocyanate had almost disappeared, 2.08 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further continued at 120 ° C for 2 hours. It was. As a result, a solution (L1) containing the resin (A) was obtained. The molecular weight of the polymer produced was Mn = 21600 and Mw = 89100 as measured by GPC.

[0182] [Example 2]

In a reaction vessel equipped with a stirrer, thermometer, and condenser, hydrogenated dimer diol (trade name: 36 carbon atoms of hydrocarbon chain made by SOVERMOL908 COGNIS) as polymer polyol, 214 · 8g, and dimer isocyanate as diisocyanate compound Compound (Product name: DDI1410 COGNIS hydrocarbon chain carbon number 36) 240g and diethylene glycol monomethyl ether acetate (made by Daicel Chemical) 462g as a solvent were charged at 100 ° C for 3 hours at 110 ° C After 3 hours of reaction at 120 ° C for 3 hours and confirming that the isocyanate had almost disappeared, add isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) 2.08 g, and further react at 120 ° C for 2 hours Went. As a result, a solution (L2) containing the resin (A) was obtained. The molecular weight of the produced polymer was Mn = 19300 and Mw = 74600 as measured by GPC.

[0183] [Example 3]

In a reaction vessel equipped with a stirrer, thermometer and condenser, hydrogenated dimer diol (trade name: SOVERMOL908 COGNIS hydrocarbon number 36 carbon atoms) 53. 71 g as polymer polyol and dimer isocyanate as diisocyanate compound Compound (Product name: DDI1410 COGNIS hydrocarbon chain carbon number 36) 60. l lg, Dibutyltin oxide (manufactured by Apia Corporation) as a catalyst 0. lg and dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) 80.6 g as a catalyst were reacted at 70 ° C for 5 hours. After confirming this, 2.08 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further carried out at 70 ° C for 1 hour. As a result, a solution (L3) containing the resin (A) was obtained. The molecular weight of the produced polymer was Mn = 10700 and Mw = 36700 as measured by GPC.

[0184] [Example 4]

Hydrogenated dimer diol (trade name: SOVERMOL908 COGNIS, 36 carbon atoms in hydrocarbon chain) 510 g as a polymer polyol in a reaction vessel equipped with a stirrer, thermometer, Vigreux rectification tube with a distillation tube at the top of the column 510 g , 725 g of dimethyl carbonate (manufactured by Ube Industries) and 0.1 lg of tetraethoxytitanium were charged and heated, and methanol produced by transesterification and dimethyl carbonate azeotroped with methanol were refluxed at a bath temperature of 130 ° C for 3 hours. Reacted. Subsequently, the temperature was gradually raised to 190 ° C. over 5 hours while distilling out the dimethyl carbonate azeotroped with the produced methanol. After that, attach a dry ice-methanol trap to condense the distillate, and gradually increase the degree of decompression over 5 hours using a vacuum pump, and finally reduce the pressure to 533. IPa pressure. Further reaction was performed for 2 hours. Thereafter, the bath temperature was lowered to 110 ° C., 0.1 g of dibutyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours. The obtained polycarbonate diol had a hydroxyl value of 56.5 mg-KOH / g.

[0185] Dimerdiol-based polycarbonate diol 333 · 37g obtained in this way, dimerisocyanate compound as diisocyanate compound (trade name: DDI1 410 COGNIS hydrocarbon chain carbon number 36) 100.18g, Dibutyltin oxide (made by Apia Corporation) 0 · lg as catalyst and dimethoxyethane (made by Wako Pure Chemical Industries, Ltd.) 433. 6 g as a solvent, stirrer, thermometer, and distillation tube at the top of the tower The reaction vessel equipped with the attached Vigreux rectification tube was charged and reacted at 70 ° C for 5 hours. After confirming that the isocyanate had almost disappeared, 2.08 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. The reaction was further carried out at 70 ° C for 1 hour. As a result, a solution (L4) containing the resin (A) was obtained.

[0186] The molecular weight of the polymer produced was Mn = 9620 and Mw = 41900 as measured by GPC. I got it.

[0187] [Example 5]

Hydrogenated high-purity dimer acid EMPOL 1008 (COGNIS hydrocarbon chain 36 carbon atoms) 418 g, hydrogenated dimer diol S OVERMOL908 (COGNIS hydrocarbon chain in a reaction vessel equipped with a stirrer, thermometer, and distillation tube The carbon number of 36) 584. 7g was charged, and the reaction was conducted by distilling the generated water, heating in a 180 ° C oil bath for 3 hours, 210 ° C for 2 hours, and 230 ° C for 2 hours. . The obtained polyester polyol had a hydroxyl value of 112. lmg KOH / g.

[0188] Dimer acid, dimer diol-based polyester polyol 50g obtained in this way, dimer isocyanate compound as diisocyanate compound (trade name: DDI1410 COGNIS, hydrocarbon chain, carbon number 36) 30 .06g, Dibutyl tin oxide (manufactured by Apia Corporation) 0 · lg as catalyst and 50g of dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) as solvent, a stirrer, thermometer, and a distillation tube at the top of the column Was added to a reaction vessel equipped with a Vigreux rectification tube and reacted at 70 ° C for 5 hours. After confirming that the isocyanate had almost disappeared, 1.26 g of isobutanol (Wako Pure Chemical Industries, Ltd.) was added dropwise. Further, the reaction was carried out at 70 ° C for 1 hour. As a result, a solution (L5) containing the resin (A) was obtained.

[0189] The molecular weight of the produced polymer was Mn = 7230 and Mw = 47300 as measured by GPC.

[0190] [Example 6]

Hydrogenation dimer diol (trade name: SOVERMOL908 COGNIS hydrocarbon number 36 carbons) 40 · 61g as polymer polyol, dimer diamine (trade name: Versamine 551) as a polymer polyol in a reaction vessel equipped with a stirrer, thermometer and condenser COGNIS hydrocarbon chain carbon number 36) 12.9g, dimerisocyanate compound as diisocyanate compound (trade name: DDI1410 COGNIS hydrocarbon chain carbon number 36) 60. l lg, dibutyltin as catalyst Oxygen (manufactured by Apia Corporation) 0.05 g and dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) 80 · 6 g as a solvent were charged and reacted at 70 ° C for 5 hours, indicating that the isocyanate had almost disappeared. After confirmation, 2.08 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and further reacted at 70 ° C for 1 hour. This As a result, a solution (L6) containing the resin (A) was obtained.

[0191] The molecular weight of the produced polymer was Mn = 6580 and Mw = 39200 as measured by GPC.

[0192] [Example 7]

Hydrogenated high-purity dimer acid diarly synthesized from hydrogenated high-purity dimer acid EMPOL 1008 (COGNIS hydrocarbon chain 36 carbon atoms) and allylic alcohol in a reaction vessel equipped with a stirrer, thermometer, and distillation tube 298 · 4g, Daimeramamine (Product name: Versamine 551 C OGNIS hydrocarbon chain carbon number 36) 267. 5g was charged and 3 hours in an oil bath at 180 ° C while distilling the generated aryl alcohol 210 The reaction was carried out by heating at ° C for 2 hours and at 230 ° C for 2 hours. The obtained polyamide having terminal amino groups was poured into a stainless steel vat at 230 ° C. to solidify. Thereafter, 512 g of N-methylpyrrolidone was added and dissolved. As a result, a solution (L7) containing the resin (A) was obtained.

[0193] The molecular weight of the produced polymer was Mn = 5000 and Mw = 17500 as measured by GPC.

[0194] [Example 8]

Hydrogenation dimer diol (trade name: SOVERMOL908 COGNIS hydrocarbon number 36 carbon atoms) 136.9 g as a polymer polyol in a reaction vessel equipped with a stirrer, a thermometer, and a condenser, dimerized isocyanate conversion as a diisocyanate compound Compound (product name: DDI1410 COGNIS, hydrocarbon chain 36 carbon atoms) 112.7g, dibutyltin oxide (catalyst made by Apia Corporation) 0 · 25g as catalyst, propylene glycol monomethyl ether acetate (solvent) Daicel Chemical Co., Ltd.) 249 · 6g was charged and reacted at 70 ° C for 5 hours. As a result, a solution (L8) containing the resin (A) was obtained. The molecular weight of the produced polymer was Mn = 3380 and Mw = 10800 as measured by GPC. Since this polymer was reacted with an excess of diisocyanate, it contained 0.501 mmol / g isocyanate groups at both ends. The average value of m was 2.

[0195] [Synthesis Example 1]

In a reaction vessel equipped with a stirrer, thermometer, and condenser, a mixture of the following structural formula 20 and the following structural formula 21: 9: 1 (mass ratio) 53. 33 g, Nafion—NR50 10.0 g, 30% peracid Hydrogen peroxide 23.7 g was charged and stirred at 70 ° C for 30 hours. Thereafter, 200 ml of toluene was added, and after filtration, the solvent of the filtrate was distilled off under reduced pressure. As a result of measuring ¹ H-NMR of the residue, it was confirmed that about 80% of the double bonds were dihydroxylated.

Structural formula 20

[0196] [Chemical 31]

[0197] Structural formula 21

[0198] [Chemical 32]

[0199] [Comparative Example 1]

In a reaction vessel equipped with a stirrer, thermometer, and condenser, Kuraray polyol (trade name: Polycarbonate diol made from Kuraray, a polycarbonate diol made of 9 carbon atoms of Kuraray) is used as a polymer polyol. 130. 3g, Dismodule W (13 carbon atoms of Sumika Bayer Urethane hydrocarbon chain) as diisocyanate compound 262.4g, and propylene glycol monomethyl etherate (Daicel Chemical Co., Ltd.) 165.8g as solvent The reaction was conducted for 3 hours at 100 ° C, 3 hours at 110 ° C, and 3 hours at 120 ° C! / After confirming that the isocyanate had almost disappeared, Isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) 2. 00 g was added dropwise and the reaction was further carried out at 120 ° C for 2 hours. As a result, a solution (L1 ′) containing the resin (Α ′) was obtained.

[0200] The molecular weight of the produced polymer was Μη = 10500 and Mw = 53200 as measured by GPC.

[0201] <Preparation of sample solution for flame retardancy test 1>

As a defoaming agent, SN deformer 4 was added to 50 parts by mass of the resin solution (L1) produced in Example 1. 70 (manufactured by San Nopco Co., Ltd.) 0 · 34 parts by mass were added and mixed uniformly using a spatula to prepare a resin solution 1A.

[0202] The resin solutions produced in Examples 2 to 8 and Comparative Example 1 were also added with an antifoaming agent as shown in Table 1, and mixed uniformly using a spatula to obtain a resin solution of 2 to Resin solution 8Α and resin solution la were prepared.

[0203] <Preparation of sample solution for flame retardancy test 2>

The resin solution (L1) produced in Example 1 was added to 15 parts by mass of OP935 (trade name) manufactured by Clariant Japan Co., Ltd. as a phosphorus-containing organic compound and 50 parts by mass of the resin solution. Name: ² Kneading was performed using a 30-type transmission-type bench roll BR-230V (manufactured by IMETTAS). Furthermore, 0.34 parts by mass of SN deformer 470 (manufactured by San Nopco Co., Ltd.) was added to this kneaded mixture, and mixed uniformly using a spatula to prepare composition 1B.

[0204] As shown in Table 1, a phosphorus-containing organic compound was added to the resin solutions produced in Examples 2 to 6 and Comparative Example 1, and a three-roll mill (trade name: Kneading was performed using a 230 type transmission bench tool BR-230V, manufactured by IMETTAS. Furthermore, the antifoaming agent shown in Table 1 was added, and the mixture was uniformly mixed using a spatula to prepare Composition 2B to Composition 6B and Composition lb.

[0205] [Table 1]

() 齄) Finally ^ cs

Compound prepared in Synthesis Example 1 57.5 parts by mass, dimer isocyanate compound (trade name: DDI1410 manufactured by COGNIS) 120 parts by mass, dibutyltin dilaurate 1.6 parts by mass, silica (trade name: Aerosil 380PE, Nippon Aerosil) 6.8 parts by weight and 30 parts by weight of diethylene glycol monoethyl ether acetate were added, and this blend was added to a three-roll minor (trade name: 230-type variable speed bench roll BR-230V, Imettas Co., Ltd.) Kneading). Furthermore, SN Deformer 470 (manufactured by Sannopco Co., Ltd.) 2.05 parts by mass is added to this kneaded compound as an antifoaming agent, and mixed uniformly using a spatula to prepare composition 1C did.

[0207] The molecule having four hydroxyl groups in one molecule contained in the compound produced in Synthesis Example 1 corresponds to "at least one kind of compound (F)", that is, this molecule is a curing agent ( As a functional group capable of reacting with the functional group of G), it has 4 hydroxyl groups in one molecule. DDI1410 corresponds to the hardener (G) and has two isocyanate groups in one molecule.

[Examples 10 to; 13] Preparation of sample solution for flame retardancy test and long-term insulation reliability test

(Production of composition (C))

Compositions as shown in Table 2 were prepared in the same manner as described above to prepare Composition 2C to Composition 5C.

[0209] [Example 14] Preparation of sample solution for flame retardancy test and long-term insulation reliability test (Production of composition (B))

Compositions as shown in Table 2 were prepared in the same manner as described above to prepare Composition 6C. The resin synthesized in Example 8 corresponds to the resin (Α ′), the average value of m is 2, the compound manufactured in Synthesis Example 1 corresponds to the curing agent (E), and the average value of n Was 3.6.

[0210] [Table 2]

) Made

It was applied to a polyimide film (trade name: Kapton 100H, manufactured by Toray DuPont Co., Ltd.) so as to be (after drying), and dried at 80 ° C. for 30 minutes using a hot air circulating dryer. Next, apply it to the opposite side of the polyimide film (trade name: Kapton 100H, manufactured by Toray DuPont Co., Ltd.) in the same way, and dry it with a hot air circulation dryer at 80 ° C for 30 minutes. The test piece applied on both sides of the polyimide film was obtained. Using this test piece, it was evaluated according to the UL94 VTM method. The results are shown in Table 1.

[0212] In addition, each of the compositions 1C to 6C was printed on a polyimide film (trade name: Kapton) using a 200-mesh stainless steel screen by a screen printing method so that the thickness was 20 m on one side (after drying). 100H, Toray 'applied to DuPont Co., Ltd.), 1 ² 0 min 1 ² 0 ° C, and dried using a hot-air circulating dryer. Next, apply it on the opposite side of the polyimide film (trade name: Kapton 100H, manufactured by Toray DuPont Co., Ltd.) in the same way, and dry it using a hot air circulation dryer at 120 ° C for 120 minutes. A test piece applied to both sides of the polyimide film was obtained. Using this test piece, it was evaluated according to the UL94 VTM method. The results are also shown in Table 2.

[0213] The results of evaluation according to the UL94 VTM method are described as follows.

[0214] 〇; VTM-0 meets flame retardant standards.

[0215] X; VTM— Does not meet the flame retardant standard of 0.

[0216] <Evaluation of long-term insulation reliability>

Flexible copper-clad laminate (trade name: UPISEL-N ΒΕ1310 (commercial name: UPISEL-N ΒΕ1310) using a 200-mesh stainless steel screen plate with a composition of 1C to 6C to a thickness of 15 πι (after drying). Grade name), manufactured by etching Ube Industries Co., Ltd.) and applied to a comb-shaped substrate (copper wiring width / copper wiring width = 50 11 m / 5011 m) (excluding wiring connections), 80 ° C For 30 minutes using a hot air circulating dryer. Subsequently, a test piece was prepared by heating at 120 ° C for 2 hours.

[0217] Using this test piece, a bias voltage of 100V was applied, and a constant temperature and humidity test under the conditions of a temperature of 85 ° C and a humidity of 85% RH was performed. MIGRATION TESTER MODEL MIG-8600 (I MV Co., Ltd.) ). Table 3 shows the resistance values 500 hours and 1000 hours after the start of the temperature and humidity test. [Table 3]

[0219] From the results of Table 1 and Table 2, it was confirmed that the resin of the present invention and the cured product of the present invention have UL94 VTM 0 flame retardancy.

[0220] Further, from the results of Table 3, it was confirmed that the cured product of the present invention had good electrical insulation in the evaluation of long-term insulation reliability.

Claims

The scope of the claims

[1] A resin having a molecular chain in which a plurality of organic groups represented by the following formula (I) are bonded, and having a weight average molecular weight of 10,000 to 300,000.

[Chemical 1-— (I)

(In the formula, C is a divalent organic group having a divalent hydrocarbon chain having 30 to 50 carbon atoms, and A is an amide bond, an ester bond, a urethane bond, a urea bond, or a carbonate bond.) o

[2] The C is a polyol having a hydrocarbon chain having 30 to 50 carbon atoms, a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms, or a polyacid having no hydrocarbon chain having 30 to 50 carbon atoms. The resin according to claim 1, wherein the resin is derived from water, a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms, or a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms.

[3] The resin according to claim 1 or 2, wherein the C is an organic group having a cyclohexane ring and / or a cyclohexene ring.

[4] The method for producing a resin according to any one of claims 1 to 3, wherein at least one of the following reactions (a) to (j) is accompanied.

( _a ) a polycondensation reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms or an ester of a lower alcohol of the polycarboxylic acid (esterification or Transesterification).

(b) A polycondensation reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

(c) A polyaddition reaction involving a decarboxylation reaction between a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid having a hydrocarbon chain having 30 to 50 carbon atoms.

(d) A polyaddition reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms.

(e) a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a hydrocarbon having 30 to 50 carbon atoms Polyaddition reaction with polyisocyanate having an elementary chain.

(f) Reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and dialkyl carbonate or diaryl carbonate, or a reaction between a polyol having a hydrocarbon chain having 30 to 50 carbon atoms and phosgene Polycarbonate formation reaction.

(g) Polyurea formation reaction by reaction of polyamine having a hydrocarbon chain of 30 to 50 carbon atoms with phosgene.

(h) A polycondensation reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms.

(i) A polyaddition reaction involving a decarboxylation reaction between a polyisocyanate having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid anhydride having a hydrocarbon chain having 30 to 50 carbon atoms.

(j) An ester amide exchange reaction between a polyamine having a hydrocarbon chain having 30 to 50 carbon atoms and a polycarboxylic acid ester having a hydrocarbon chain having 30 to 50 carbon atoms.

[5] A composition comprising, as an essential component, the resin according to any one of claims 1 to 3, and a curing agent having a functional group capable of reacting with the resin.

The resin is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group and a primary or secondary amino group, and has reactivity with the curing agent. It is a resin composed of molecules having m functional groups in one molecule, and the curing agent has n functional groups capable of reacting with the resin in one molecule, and is a hydrocarbon having 30 to 50 carbon atoms. It is a curing agent consisting of molecules with chains

[6] Polyol having 30 to 50 hydrocarbon chains, 3 or more hydroxyl groups in one molecule, 3 to 30 hydrocarbon chains having 30 to 50 carbon atoms in one molecule A polycarboxylic acid having the above carboxyl group, a polyanhydride having a hydrocarbon chain having 30 to 50 carbon atoms, a hydrocarbon chain having 30 to 50 carbon atoms, and 3 or more isocyanate groups in one molecule. A compound selected from the group of polyamines having a polyisocyanate and a hydrocarbon chain having 30 to 50 carbon atoms and having 3 or more primary or secondary amino groups in one molecule, and having a functional group At least one compound capable of reacting with the curing agent described below, An essential component is at least one curing agent having two or more functional groups capable of reacting with the compound in a molecule and a hydrocarbon chain having 30 to 50 carbon atoms.

The composition characterized by the above-mentioned.

7. The composition according to claim 5 or 6, further comprising a phosphorus-containing organic compound.

[8] A cured product obtained by curing the composition according to any one of claims 5 to 7.

[9] The cured product according to claim 8, wherein the cured product exhibits VTM-0 flame retardancy in a flame retardancy test by UL94 VTM method.