JP3389093B2 - Thermoreversible crosslinked polymer and its use - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates to a hot melt resin comprising this crosslinked polymer with a novel thermoreversible crosslinked polymer.

[0002]

2. Description of the Related Art Thermoplastic resins are widely and conveniently used in the world because they are melted when they are heated at a high temperature and can be molded and have a strength that can withstand use when the temperature drops. There is. However, in general, the viscosity of a thermoplastic resin when heated and melted sufficiently satisfies the molding processability, but since the strength and heat resistance of the thermoplastic resin at the operating temperature are not high, the range of use of the thermoplastic resin is limited. Are limited.

Block polymers represented by SIS (styrene-isoprene-styrene) have a high Tg at room temperature.
Polymer blocks gather to form a pseudo-crosslinked structure,
At a temperature of Tg or higher, the pseudo-crosslinking structure is destroyed and the viscosity is lowered to a value that allows processing and molding. Therefore, the molding processability at a relatively high temperature and the strength and heat resistance at a use temperature are compatible with each other, but since the pseudo-crosslinked structure is governed by the Tg of the polymer itself, the heat resistance is essentially high. There is a shortage problem.

[0004]

[Problems to be Solved by the Invention] A full-scale thermoreversible cross-linking structure, that is, a cross-linking structure that recovers when the temperature rises and the cut temperature decreases, is introduced into the thermoplastic resin to obtain the above-mentioned thermoplastic resin. Many proposals have been made to solve problems. But both have problems. JP-A-50-139135 and JP-A-51-1903.
Japanese Patent Publication No. 5 discloses a thermoplastic resin obtained by crosslinking an acrylic polymer having a carboxyl group with a metal ion. JP-A-56-14573 discloses a thermoplastic resin obtained by adding maleic anhydride to low molecular weight polyisoprene and crosslinking it with metal ions. Further, JP-A-5-202345 discloses a thermoplastic resin composed of an acrylic polymer having a carboxyl group neutralized with a polyvalent metal. Thermoplastic resins containing these metal crosslinked structures are superior in heat resistance to block polymers typified by SIS, but have high melt viscosity upon heating (since metal ion crosslinking is relatively strong, heating Even if it is difficult to break the bridge)
And the thermal stability when heated is low (especially when ester groups are present in the polymer, the metal plays a catalytic role to form crosslinks between the organic polymers, and the covalent bonds are gradually formed between the organic polymers. (Due to the formation), there is a problem that the melting temperature gradually rises.

JP-A-58-125774 discloses a thermoplastic resin containing an acrylic polymer having a carboxyl group neutralized with a polyvalent metal and o-methoxyarylic acid. This thermoplastic resin is effective in that the melt viscosity decreases when heated as compared with the general metal ion crosslinked body as described above, but the melt viscosity of the crosslinked body is too high as compared with non-crosslinked ones. However, since the covalent bond is gradually formed by heating, there is a problem that the thermal stability at the time of heating is poor.

JP-A-52-65549 describes a thermoplastic resin comprising a mixture of a polymer containing an acid group and a polymer containing an amino group. JP-A-56-
Japanese Patent No. 57865 describes a thermoplastic resin obtained by copolymerizing (meth) acrylamide and an olefinic unsaturated mono- or dicarboxylic acid. JP-A-57-15
Japanese Patent No. 8275 describes a thermoplastic resin containing an acrylic polymer having an amino group in the molecule and a carboxyl group at the molecular end as a main component. Thermoplastic resins utilizing ionic crosslinks formed between these acids and amino groups also have high melt viscosity because the ionic crosslinks formed are strong and the crosslinks are hard to break even when heated. Since irreversible amide bonds are formed between them, there is a problem in that the thermal stability during heating is low in this case as well.

In view of the above circumstances, an object of the present invention is to provide a thermoreversible crosslinked polymer having a sufficiently low melt viscosity upon heating and excellent stability of the melt viscosity, and a hot melt containing the same. To provide a resin.

[0008]

Means for Solving the Problems As a result of various studies and studies for solving the above problems, the inventors have found that amino group-containing groups that form thermoreversible ionic crosslinks formed between an acid group and an amino group. Hindered structure (steric hindrance structure) as a compound
When an amino group-containing compound having is used, the melt viscosity upon heating is sufficiently low, the thermal stability is also good, and
It has been found that a thermoreversible crosslinked polymer having excellent heat resistance and strength at use temperature can be obtained.

The reason why such a phenomenon occurs is presumed as follows. Due to steric hindrance, the hindered structure prevents the acid group and the amino group from approaching each other and forms an ionic crosslink with a proper distance, so the crosslink is easily broken by heating, and the heat irreversible Also prevents the formation of typical amide bonds
Ingredients that can be. Therefore, the thermoreversible crosslinked polymer according to the present invention comprises a part based on the compound (A) having two or more acid groups in one molecule and two or more hinders in one molecule.
A portion based on the compound (B) having a Doamino group,
Acid group of compound (A) and hin of compound (B)
Ri Na is attached via a cross-linked structure derived from the reaction with Dadoamino groups, small of compounds (A) and (B)
Kutomo While in polymer der Ru crosslinked polymer, the reduction
Compound (A) is a carboxylic acid having a valence of 2 or more and a sulfonated compound.
Products, polyester compounds, polyepoxy compounds,
A) Acrylic polymer, styrene polymer, styrene
Block polymer, diene polymer, olefin
Polymer, ethylene-vinyl acetate polymer
It is at least one selected, and the cross-linked structure is a compound
Comprising a structure having a steric hindrance from hindered group of the object (B), the crosslinking polymer is broken the bond between cross-linked structure is heated, binding of the cross-linked structure temperature drops
Shows the thermoreversible property that the bond is restored ,
The melt viscosity of the cross-linking polymer when the bond is broken is, the melt viscosity of the higher one of the melting viscosity of when compound (A) and the compound (B) is heated at the same temperature when it is alone, respectively It is characterized in that it is reduced to less than twice.

[0010] The melt viscosity of the thermally reversible crosslinked polymer when the bond is broken crosslinked structure with pressurized heat, when the compound (A) and the compound (B) is heated at the same temperature when it is alone, respectively It is preferable to lower the melt viscosity to the higher one of the melt viscosities shown, since the molding processability becomes essentially excellent.

[0011] group with a compound having the compound (A) (B)
Hindered possessed by - the molar ratio of Doamino group (acid group / hindered -
The amino group) can be 0.1-10 . Although not particularly limited, the (meth) acrylic polymer in the compound (A ) is preferably a block polymer. This is because the heat resistance is essentially excellent.

The hot melt resin according to the present invention contains the above-mentioned thermoreversible crosslinked polymer .

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the compound (A )
Is a compound having two or more acid groups in one molecule ,
From the viewpoint of forming a bridge structure, an acid group is included in one molecule.
It is preferable to contain three or more. An acid group is
It is a silyl group, a sulfonic acid group or a phosphoric acid group. Specifically
Is a compound (A) is a divalent or higher carboxylic acid, sulfone
Acid compound, polyester compound, polyepoxy compound,
(Meth) acrylic polymer, styrene polymer,
Tylene type block polymer, diene type polymer, olefin
Among vinyl polymers and ethylene-vinyl acetate polymers
It is at least one selected from I.e.
It is each compound shown. Malonic acid, succinic acid, 1,1-cyclopropanedicarboxylic acid, 1,3-acetonedicarboxylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, isophthalic acid, phthalic acid , Terephthalic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
1,2-benzenedisulfonic acid, 1,3-benzenedisulfonic acid, aconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,
Dicarboxylic or higher carboxylic acid such as 3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, sulfonic acid compound ; Polyester compound having carboxylic acid at molecular end; Polyepoxy compound having carboxyl group introduced by reacting epoxy group and / or hydroxyl group of epoxy compound with polyvalent carboxylic acid; (meth) acrylic acid, maleic acid, itacco
Acid, allyl acetic acid, 2-sulfoethyl (meth) acryl
-To, 2-acrylamido-2-methylpropane sulfo
Acid, β- (meth) acryloyloxyethyl hydro
Gensuccinate, β- (meth) acryloyloxy
Ethyl hydro Jenfu sauce - DOO, Metakuriroirue Ji
Α, β-unsaturated carboxylic acids such as luphosphate, α,
1 β-unsaturated sulfonic acid or α, β-unsaturated phosphoric acid
(Meth) acrylic polymer synthesized as two copolymerization components
Limer ; a styrene-based polymer having the above α, β-unsaturated carboxylic acid, α, β-unsaturated sulfonic acid or α, β-unsaturated phosphoric acid as one copolymerization component; Styrenic block polymer having a carboxyl group introduced; copolymerized with the above α, β-unsaturated carboxylic acid, α, β-unsaturated sulfonic acid or α, β-unsaturated phosphoric acid, or added with maleic anhydride. A diene-based polymer having a carboxyl group introduced thereinto; an olefin-based polymer obtained by copolymerizing the above α, β-unsaturated carboxylic acid, α, β-unsaturated sulfonic acid or α, β-unsaturated phosphoric acid; The above α, β-unsaturated carboxylic acid,
alpha, beta-unsaturated sulfonic acids or alpha, ethylene was copolymerized with beta-unsaturated phosphoric acid - vinyl acetate polymers; Ru thermoplastic polymer der such.

The (meth) acrylic polymer used in the present invention is at least one of the above α, β-unsaturated carboxylic acid, α, β-unsaturated sulfonic acid and α, β-unsaturated phosphoric acid. 1 of the polymers synthesized by using as a copolymerization component
And α, β-unsaturated carboxylic acid is (meth) acrylic acid, and alkyl (meth) acrylate having 1 to 30 carbon atoms, hydroxyethyl (meth) acrylate,
It is a polymer synthesized by radical polymerization using a (meth) acrylate-based monomer such as hydroxypropyl (meth) acrylate or ethoxyethyl (meth) acrylate as a copolymerization component.

Examples of the (meth) acrylic polymer include styrene monomers such as α-methylstyrene, vinyltoluene and styrene; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; fumaric acid and fumaric acid. Mono- or dialkyl esters of acids; maleic acid, mono- or dialkyl esters of maleic acid; itaconic acid, mono- or dialkyl esters of itaconic acid; (meth) acrylonitrile,
It may be a polymer synthesized by using other monomers such as butadiene, isoprene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, vinyl pyridine and vinyl carbazole as a copolymerization component.

In the present invention, the compound (B ) has a bulky substituent (having steric hindrance) on one or both of the atoms to which the amino group is bonded, so that the compound between the acid group and the amino group is A compound with a structure that interferes with the amide bond formation reaction , that is, two or more compounds in one molecule.
It is a compound having a hindered amino group . Specific examples include compounds having a 2,2,6,6-tetramethylpiperidinyl group or a 2,2,6,6-tetramethyl-4-piperidinol group, and more specifically, , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-
4-piperidyl) sebacate, tetrakis (2,2,2
6,6-Tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-)
Tetramethyl-4-piperidyl) butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butane tetracarboxylate, bis (1,2,2,
6,6-Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-Tetramethyl-4-piperidinole / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4
-Piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,6-bis (2,2,6,6)
-Tetraethyl-4-piperidylamino) hexane /
2,4-Dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiary Octylamino-s-triazine polycondensation product,
1,5,8,12-Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,
5,8,12-Tetraazadodecane, 1,5,8,12
-Tetrakis [2,4-bis (N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12
-Tetraazadodecane, 1,6,11-tris [2,4
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
2,2, such as 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane
An ester compound or a partial ester compound of 6,6-tetramethyl-4-piperidinol and a divalent to tetravalent carboxylic acid, 2,2,6,6-tetramethyl-4-piperidylamine and cyanuric chloride If desired, a condensate with a polyvalent amine or N, N-bis (2,2,6,6-
A condensate of tetramethyl-4-piperidyl) alkylenediamine with cyanuric chloride and optionally an alkylamine; 2,2,6,6-tetramethyl-4-piperidinyl (meth) acrylate, etc., 2,2,6 , A polymer obtained by copolymerizing a monomer having a 6-tetramethylpiperidinyl group or a 2,2,6,6-tetramethyl-4-piperidinol group; and the like.

The thermoreversible crosslinked polymer thus obtained has a physical property of 3
It is preferable to use a compound containing a secondary hindered amino group rather than a compound containing a secondary hindered amino group. The acid group-containing compound (A) and the hindered amino group-containing compound
(B) needs to be melted at a high temperature. The high temperature referred to here is a temperature at which a thermoplastic resin is generally processed, and is preferably 100 to 250 ° C.

The molecular weight of the acid group-containing compound (A) and the hindered amino group-containing compound (B) is not particularly limited as long as it can be melted at a high temperature. A high molecular weight material of about, 000,000 can be used. The ratio of the melt viscosity of the thermoreversible crosslinked polymer according to the present invention at high temperature to the higher melt viscosity of the compound (A) and the compound (B) at the same temperature (thermoreversible crosslinked polymer viscosity / The compound viscosity) is 2 or less, preferably 1.5 or less, and more preferably 1 or less. A conventional crosslinked product using ionic crosslinking has a high viscosity because the ionic crosslinking is difficult to break even in a molten state, and the melt viscosity ratio before and after crosslinking exceeds 10.

Acid group-containing compound (A) used in the present invention
The acid group and the amino group of the hindered amino group-containing compound (B) have a molar ratio (acid group / amino group) of preferably 0.1 to 10, and more preferably 0.3 to 3.0. More preferable. If it deviates from this range, the desired heat resistance will be difficult to be exerted because there are too few crosslinking points, or there will be many molecules not involved in crosslinking due to the excess of either one, and conversely heat resistance. Is likely to occur. In addition, 0.
When it is 3 to 3.0, it is possible to efficiently crosslink.

[0020]

EXAMPLES Examples within the scope of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. In the following, "%" means "% by weight" and "part" means "part by weight". In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated by gel permeation method.
It was calculated as a polystyrene conversion value by ion chromatography (GPC).

The characteristics of the crosslinked polymer were measured by the following methods. (Sample preparation) The cross-linked polymer was applied to the GPD coater (Yuri
(Made by Le Machine Co., Ltd.), so that the coating thickness is 25 μm.
The ET film was melt-coated and used as a sample. (Holding power) A sample was attached to a stainless steel plate with an adhesive area of 25 mm x 25 mm, and was crimped back and forth once with a 2 kg roller, and the temperature was adjusted at a predetermined temperature (80 ° C) for 30 minutes each. Time to drop under load or 2
The deviation (unit: mm) after 4 hours was measured. Heat resistance is
The longer it takes to drop, or the smaller the deviation after 24 hours, the better.

(Viscosity at 180 ° C.) Flow Tester-CFT
Using -500C (manufactured by Shimadzu Corporation), the temperature was 180 ° C., the load was 10 kgf / cm ² , and the die shape was 0.5 mmφ × 1 mm. The viscosity after removing the solvent was measured by using the polymer solution treated with a vacuum dryer at 180 ° C. for 1 hour. (Example 1) 175.5 g of methyl methacrylate and 3.6 g of acrylic acid were placed in a 2-liter four-necked flask equipped with a stirrer, a nitrogen introducing tube, a dropping funnel, a thermometer, and a cooling tube.
0.9 g of tetraethylene glycol diacrylate and 140 g of ethyl acetate were added, and the temperature was raised to 85 ° C under a nitrogen atmosphere. After the internal temperature reached 85 ° C., 3 g of pentaerythritol tetrakisthioglycolate, 2′2-azobis (2-methylbutyronitrile (ABN-E, manufactured by Nippon Hydrazine Industry Co., Ltd.) 0.54 g, acetic acid 20 g of ethyl was added to start the polymerization, and pentaerythritol tetrakisthioglycolate of 1.5 and 50 minutes after the start of the polymerization, respectively.
g, ABN-E 0.27 g, and ethyl acetate 10 g were added. After 140 minutes, the degree of polymerization of methyl methacrylate was 81.
It had reached 8%. Then, 411.6 g of butyl acrylate and 8.4 acrylic acid were added to the reaction solution from a dropping funnel.
g and ethyl acetate 400 g were added dropwise over 2 hours. 30 minutes and 60 minutes after the end of dropping, ABN-E0.18
g and 5 g of ethyl acetate were added. After a further 60 minutes, 0.6 g of azobisisobutyronitrile and 10 g of ethyl acetate were added. After reacting for 2 hours under reflux, the reaction was terminated by cooling to room temperature to obtain an acrylic star block polymer containing an acid group. The resulting star block polymer had a number average molecular weight (Mn) of 26,900 and a weight average molecular weight (Mw) of 150,000.

To 100 parts of this star-shaped block polymer (as calculated as solid content), 5.49 parts of ADEKA STAB LA-57 (made by Asahi Denka Co., Ltd.) which is a hindered amine was added and mixed well, and the mixture was put into a vacuum dryer. The solvent was removed to obtain a light yellow transparent thermoreversible crosslinked polymer . Example 2 A thermoreversible crosslinked polymer was obtained in the same manner as in Example 1 except that the kind of the hindered amino group-containing compound added was changed . (Example 3) Methyl methacrylate 167.8 g, ADEKA STAB LA-87 (Asahi Denka Kogyo Co., Ltd.) were placed in a 2-liter four-necked flask equipped with a stirrer, a nitrogen introducing tube, a dropping funnel, a thermometer, and a cooling tube. (Produced), 11.2 g of tetraethylene glycol diacrylate, and 140 g of ethyl acetate were added, and the temperature was raised to 85 ° C. under a nitrogen atmosphere. After the internal temperature reached 85 ° C., 3 g of pentaerythritol tetrakisthioglycolate,
ABN-E (Nippon Hydrazine Kogyo) 0.54 g, were added to start polymerization ethyl acetate 20g. Start of polymerization 50
Minutes and 80 minutes later, pentaerythritol tetrakisthioglycolate 1.5 g, ABN-E 0.27 g,
10 g of ethyl acetate was added. After 120 minutes, the degree of polymerization of methyl methacrylate reached 77.2%. Then, 393.8 g of butyl acrylate was added to the reaction solution from a dropping funnel,
26.2 g of ADEKA STAB LA-87 (manufactured by Asahi Denka Kogyo),
400 g of ethyl acetate was added dropwise over 2 hours. After 30 and 60 minutes from the completion of dropping, ABN-E (0.18 g) and ethyl acetate (5 g) were added, respectively. After a further 60 minutes, 0.6 g of azobisisobutyronitrile and 10 g of ethyl acetate were added. After reacting for 2 hours under reflux, the reaction was terminated by cooling to room temperature to obtain an acrylic star block polymer containing a hindered amino group. The star block polymer thus produced had an Mn of 5,700 and a weight average molecular weight Mw of 12,8.
It was 00.

[0024] The star block polymer - relative solution 100 parts, pyromellitic acid added thereto and mixed well 0.59 parts, vacuum drier solvent was removed yellow thermoreversible crosslinking heavy
To obtain a case body. (Example 4) Example 3 except that the type of the acid group-containing compound to be added was changed.
A thermoreversible crosslinked polymer was obtained in the same manner as in. Example 5 To 100 parts of the hindered amino group-containing star block polymer synthesized in Example 3, 100 parts of the acid group-containing star block polymer synthesized in Example 1 was added and mixed well. The solvent was removed by a vacuum dryer to obtain a light yellow transparent thermoreversible crosslinked polymer . (Comparative Examples 1 and 2) The non-crosslinked star block polymers synthesized in Examples 1 and 3 were used as comparative examples. (Comparative Examples 3 to 6) Thermoreversible crosslinked polymers were obtained in the same manner as in Example 1 except that the compounds shown in Tables 3 and 4 were used.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

The thermoreversible crosslinked polymers of Examples 1 to 5 above,
Polymers of Comparative Examples 1 and 2 and Comparative Crosslinks of Comparative Examples 3-6
The holding power at 80 ° C and the viscosity at 180 ° C of the polymer are shown in Tables 1 to 4. As can be seen from the measurement results of Examples 1 and 2 and Comparative Example 1, the thermoreversible crosslinked polymers of Examples 1 and 2 were compound (A).
Because of the ionic cross-linking formed between the acid group of (1) and the amino group of hindered amine, the holding power at 80 ° C. is greatly improved as compared with the compound (A ) containing no hindered amine. In addition, 1 of the thermoreversible crosslinked polymers of Examples 1 and 2
The viscosity at 80 ° C was lower than that of the compound (A) to which no hindered amine was added, and it can be seen that the crosslinking was completely broken. The reason that the melt viscosity of the thermoreversible crosslinked polymer is lower is that the free and melted hindered amine contained in the thermoreversible crosslinked polymer functions as a plasticizer. This is the preferred form.

As can be seen from the measurement results of Examples 3 and 4 and Comparative Example 2, the thermoreversible crosslinked polymers of Examples 3 and 4 were obtained by using the hindered amino group of compound (B ) and the acid group of polyvalent carboxylic acid. Due to the ionic cross-linking formed between and, the holding power at 80 ° C. is greatly improved as compared with the case where no polyvalent carboxylic acid is added. The melt viscosity of the thermoreversible crosslinked polymer is
In Example 3, although it is higher than that of the compound (B 1 ) to which the polycarboxylic acid is not added, it is understood that the crosslinking is relatively easy to break.

As can be seen from the measurement results of Example 5 and Comparative Examples 1 and 2, the thermoreversible cross-linked polymer of Example 5 has an acid group of compound (A ) and a hindered amino group of compound (B ) . Due to the ionic crosslinks formed between the compounds (A 2 ) ,
(B ) The holding power at 80 ° C. is greatly improved as compared with each of them alone. Further, the 180 ° C. viscosity of the thermoreversible crosslinked polymer of Example 5 was lower than that of the compound (A), which has a higher viscosity of both (A) and (B), and it was found that the crosslinking was completely broken. .

The composition using the metal crosslink of Comparative Example 3 is superior to the thermoreversible crosslinked polymer of Example 1 in holding power at 80 ° C., but has a 180 ° C. viscosity of Comparative Example 1 before crosslinking. It is very high as compared with the above, and it can be seen that the crosslinking is not completely broken at high temperature. In the system in which o-methoxybenzoic acid was added to the metal crosslinked product of Comparative Example 4, 180 compared with Comparative Example 3.
Although the viscosity at ℃ is considerably low, it is still much higher than the viscosity of the resin before crosslinking, and it can be seen that the crosslinking is not completely broken even at high temperatures.

The cross-linked polymer using the primary diamine of Comparative Example 5 is inferior to that of Examples 1 and 2 although the holding power at 80 ° C. is slightly improved. Further, it can be seen that the viscosity is extremely high at 180 ° C. and the cross-linking is difficult to break. In addition, Comparative Example 3
In ~ 5, the viscosity was gradually increased by heating and finally gelled.

It can be seen that the crosslinked polymer using the tertiary diamine of Comparative Example 6 did not show improvement in holding power at 80 ° C. and did not form ionic crosslinks.

[0035]

INDUSTRIAL APPLICABILITY In the thermoreversible crosslinked polymer and hot melt resin according to the present invention, a thermoreversible crosslinked structure is represented by, for example, ionic crosslinking formed between an acid group and an amino group of a hindered amino group. As described above, since the structure has a steric hindrance, the melt viscosity at the time of heating is sufficiently low, and the stability of the melt viscosity is also excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (5)

(57) [Claims] 1. A moiety based on the compound (A) having two or more acid groups in one molecule, and two or more hinders in one molecule.
A portion based on the compound (B) having a Doamino groups, of
Acid group of compound (A) and hinder of compound (B)
Ri Na is attached via a cross-linked structure derived from the reaction with Doamino groups, less of the compound (A) and the compound (B)
In crosslinked polymers also one is Ru polymer der and the compound (A) is a divalent or higher carboxylic acids, sulfonic
Acid compound, polyester compound, polyepoxy compound,
(Meth) acrylic polymer, styrene polymer,
Tylene type block polymer, diene type polymer, olefin
Among vinyl polymers and ethylene-vinyl acetate polymers
It is at least one selected from the crosslinked structure, hindered amine to the compound (B)
Heat that comprises a structure having a steric hindrance from amino group, the crosslinked polymer, broken bond with the crosslinking structure is heated, binding of the cross-linked structure temperature drops returns
Shows the reversibility, the melt viscosity of the cross-linking polymer when the bond is broken crosslinked structure in heating, shown when the compounds (A) and (B) are heated at the same temperature when it is alone, respectively It decreases to below 2 times the melt viscosity of the higher one of the melting viscosity, thermally reversible crosslinked polymer, characterized in that. The melt viscosity of the thermally reversible crosslinked polymer when the bond is broken in 2. A crosslinking at elevated heat structure, compound (A) and the compound (B) is heated at the same temperature when it is alone, respectively It decreases to below the melt viscosity of higher ones of the melt viscosity of the time, thermoreversible crosslinked polymer of claim 1. 3. An acid group possessed by the compound (A) and the compound (B)
Hindered possessed by - the molar ratio of Doamino group (acid group / hindered -
Doamino group) is 0.1 to 10, according to claim 1 or 2
The thermoreversible crosslinked polymer described in 1. Wherein (meth) acrylic polymer - block polymers - a thermoreversible crosslinked polymer of claim 1. 5. A hot melt resin containing the thermoreversible crosslinked polymer according to any one of claims 1 to 4 .