JP3191154B2 - Copolyester resin for flame-retardant adhesive and laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymerized polyester resin for a flame-retardant adhesive and a laminate using the same. More specifically, the present invention relates to a polyester resin in which a phosphorus-containing carboxylic acid compound having a specific structure is copolymerized, and a laminate using the polyester resin as an adhesive layer between a metal plate and a PET film (or a PET sheet).

[0002]

2. Description of the Related Art Conventionally, as a method of imparting flame retardancy to a copolymerized polyester resin, a halogen-based flame retardant and a flame retardant auxiliary such as antimony trioxide are mixed with the resin, or a monomer material containing a halogen atom is used. A method of copolymerizing in a resin or the like is used. However, although these methods can achieve the intended imparting of flame retardancy, environmental impacts such as toxicity of the halogen-based flame retardant and the flame-retarded copolymer resin itself and desorption of halogen during incineration can be achieved. It is pointed out that the resin is large, and at present, the flame-retarded resin according to the present method has not been used much.

On the other hand, there has been proposed a method of imparting flame retardancy by mixing a phosphorus-based substance with a copolymerized polyester resin. At this time, in order for the resin to exhibit a high degree of flame retardancy, it depends on the resin used and the required degree of flame retardancy. It is necessary to mix at a ratio of about 20% by weight. For this reason, when these flame-retarded resins are used as an adhesive by dissolving them in a solvent, a part of the phosphorus-based substance settles and the storage stability of the coating liquid is reduced, or the adhesive strength is reduced. Was not enough. Also, when these flame-retarded resins are melt-extruded to apply an adhesive layer,
There is a problem that the melt viscosity of the resin itself rises remarkably, and it is difficult to obtain sufficient adhesive strength.

On the other hand, there has been proposed a method of imparting flame retardancy to a resin by copolymerizing a monomer material containing a phosphorus atom with a polyester resin (Japanese Patent Publication No. 55-41610).
No.). However, the method disclosed herein is a method for producing a flame-retardant copolymerized polyester capable of forming a molded article such as a fiber, a film, and a board. Not something. Also,
JP-B-63-3913 proposes a polyester adhesive having flame retardancy. However, the resin disclosed herein is a resin obtained by copolymerizing a monomer material such as 5-sodium sulfoisophthalic acid, and is used as a water-dispersible fiber treatment agent or a water-soluble adhesive. However, it is not an organic solvent-type resin for an adhesive, and cannot be suitably used as an adhesive between a metal plate and a PET film (or a PET sheet).

[0005]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art and has good adhesive strength to a metal plate and a PET film (or a PET sheet).
Another object of the present invention is to provide a copolymerized polyester resin for a flame-retardant adhesive having a low environmental load, and a laminate using the same.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, they have copolymerized a phosphorus-containing carboxylic acid compound having a specific structure and occupied the copolymerized polyester resin. It has been found that this object can be achieved by adjusting the phosphorus atom content, the glass transition temperature, and the relative viscosity to specific ranges, and the present invention has been achieved.

That is, the gist of the present invention is as follows. (1) A polyester resin composed of one or more dicarboxylic acid components and one or more glycol components, and copolymerized with a phosphorus-containing dicarboxylic acid compound represented by the following formula, wherein phosphorus in the copolymerized polyester resin is A copolymerized polyester resin for a flame-retardant adhesive, wherein the content of atoms is in the range of 0.05 to 5% by weight, the glass transition temperature is -30 to 40 ° C, and the relative viscosity is 1.1 to 1.6.

Embedded image (2) (A) of a metal plate layer selected from copper, iron, aluminum and tin, an adhesive layer (B) made of the flame-retardant copolymerized polyester resin described in (1) above, and a PET film (or P
A layered product wherein the layer (C) of the ET sheet) is present at least in this order.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The copolymerized polyester resin for a flame-retardant adhesive of the present invention (hereinafter referred to as "copolyester resin").
Is composed of one or more dicarboxylic acid components and one or more glycol components, and is obtained by copolymerizing the phosphorus-containing dicarboxylic acid compound represented by the above formula.

As the dicarboxylic acid component, terephthalic acid, isophthalic acid,
Adipic acid and sebacic acid are used. Further, if necessary, oxalic acid, malonic acid, succinic acid, azelaic acid, carboxylic dicarboxylic acid, saturated aliphatic dicarboxylic acid such as dodecanedicarboxylic acid, fumaric acid, maleic acid, unsaturated aliphatic dicarboxylic acid such as itaconic acid , (Anhydride) phthalic acid, naphthalenedicarboxylic acid diphenic acid, etc., aromatic dicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, etc., alicyclic dicarboxylic acid, etc. may be used in combination. As these dicarboxylic acid components, dialkyl ester derivatives of the above-mentioned dicarboxylic acids may be used, and it is not necessary to use one kind alone, and it is also possible to use a mixture of two or more kinds.

As the glycol component, neopentyl glycol and ethylene glycol are mainly used from the viewpoint of adhesive properties and cost. If necessary, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 -Aliphatic glycols such as pentanediol and polytetramethylene glycol, aromatic glycols such as ethylene oxide adduct of bisphenol A and ethylene oxide adduct of bisphenol S, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, etc. May be used in combination. These glycol components are not necessarily 1
It is not necessary to use a plurality of types, and it is also possible to use a mixture of a plurality of types.

The phosphorus-containing dicarboxylic acid compound represented by the above formula is used for the purpose of imparting adhesive properties and flame retardancy, and specifically, 2- (9,10-dihydro
-9-oxa-10-oxide-10-phosphophenanthrene-10
-Yl) methylsuccinic acid (hereinafter referred to as “HCA-IA”), 2
-(9,10-dihydro-9-oxa-10-oxide-10-phosphophenanthrene-10-yl) methyl succinic acid dimethyl ester, 2- (9,10-dihydro-9-oxa-10-oxide-10 -
Phosphophenanthrene-10-yl) methyl succinic acid diethyl ester, 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphophenanthrene-10-yl) methyl succinic acid ethylene side adduct, etc. However, HCA-IA is preferred in terms of adhesive properties and cost.

Further, in addition to the above-mentioned components, the copolymerized polyester resin may further comprise, as long as the properties of the present invention are not impaired,
Trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid, or anhydrides thereof, dialkyl esters, polyvalent carboxylic acid derivatives such as diphenyl esters, trimethylolpropane, pentaerythritol, polyhydric alcohols such as glycerin, ε -Caprolactone, γ-butyrolactone, p-hydroxybenzoic acid hydroxycarboxylic acid and the like may be copolymerized.

In the copolymerized polyester resin of the present invention, the phosphorus atom content determined by the method described below must be in the range of 0.05 to 5% by weight, and is preferably in the range of 1 to 5% by weight. preferable. If the phosphorus content is less than 0.05% by weight, it is difficult to impart the desired flame retardancy.
On the other hand, if the phosphorus content exceeds 5% by weight, the desired flame retardant is obtained, but the copolymerization ratio of the phosphorus-containing dicarboxylic acid compound represented by the formula is increased, and as a result, the molecular weight of the resin is increased. Is not only difficult to increase, but also the solubility of the resin in the solvent is reduced, and it is difficult to use the resin as an adhesive resin.

Further, the copolymerized polyester resin of the present invention has a glass transition temperature of -30 to 40 ° C. determined by a method described later.
, And preferably in the range of −10 to 25 ° C. If the glass transition temperature is lower than -30 ° C, it is difficult to handle the resin, and the performance as an adhesive,
Particularly, the adhesive strength in a high temperature region (50 to 120 ° C.) is reduced.
On the other hand, when the glass transition temperature is higher than 40 ° C., the solubility of the resin in a solvent decreases, and it becomes difficult to use the resin as an adhesive resin, which is not preferable.

Further, the relative viscosity of the copolymerized polyester resin of the present invention must be in the range of 1.1 to 1.6, and preferably in the range of 1.2 to 1.5. When the relative viscosity is less than 1.1, the adhesive strength decreases. On the other hand, a resin having a relative viscosity of more than 1.6 is not preferred because not only is it difficult to produce a resin, but also the solubility in a solvent is reduced.

Next, a method for producing the copolymerized polyester resin of the present invention will be described. That is, the polyester resin of the present invention uses one or more of the above-described dicarboxylic acid components, one or more of the glycol components and the phosphorus-containing dicarboxylic acid compound represented by the formula, and under normal pressure at a temperature of 200 to 28.
After direct esterification or transesterification at 0 ° C., in the presence of a conventionally known catalyst, under a reduced pressure of 5 hPa or less,
It can be produced by carrying out a melt polycondensation reaction at a temperature of 200 to 280 ° C.

At this time, as a method of adjusting the molecular weight of the copolymerized polyester resin, there are a method of stopping the polymerization at an appropriate viscosity of the polyester melt at the time of the polymerization, and a method of producing a polyester having a high molecular weight once and then preparing a depolymerizing agent ( (Acid or alcohol) and a method of adding a monofunctional alcohol or carboxylic acid in advance. Although the molecular weight of the copolymerized polyester resin of the present invention may be adjusted by any of the methods described above, a method of controlling the viscosity of a polyester melt during polymerization, that is, a method of controlling the torque of a stirrer, is suitably used. When it is desired to increase a specific functional group, it is preferable to increase the molecular weight of the polyester resin to a certain viscosity and then depolymerize with a low-molecular substance having the functional group to be increased.

As a catalyst used for producing the above-mentioned copolymerized polyester resin, a conventionally known metal compound can be used. Specifically, alkali metal compounds such as lithium oxide, lithium methylate, lithium ethylate, lithium glycolate, lithium acetate, sodium methylate, sodium ethylate, sodium glycolate, sodium formate, sodium acetate, and potassium acetate; Zinc, zinc formate, zinc acetate, zinc propionate, zinc borate, zinc glycolate, zinc benzoate, zinc caproate, zinc butyrate, zinc valerate, zinc antimonate, zinc germanate, zinc germanate, etc. Manganese compounds such as zinc compounds, manganese acetate, manganese citrate, manganese borate, manganese glycolate, and manganese antimonite; cobalt compounds such as cobalt formate, cobalt chloride, cobalt acetate, cobalt propionate, and cobalt hydroxybenzoate; acid Alkaline earth metal compounds such as calcium, calcium acetate, calcium malonate, calcium adipate, strontium acetate, barium acetate, magnesium acetate, titanium isopropoxide, titanium butoxide, titanyl ammonium oxalate, potassium titanyl oxalate, titanyl oxalate Strontium, potassium titanyl tartrate, titanyl ammonium tartrate, titanium compounds such as titanium glycolate, tetrabutyl titanate, and titanium acetyl acetate; antimony such as antimony trioxide, antimony pentoxide, antimony glycolate, antimony alcoholate, antimony acetate, and antimony phenolate Compound, germanium alcoholate, germanium phenolate,
Potassium germanate, sodium germanate, calcium germanate, potassium germanate, germanium compounds such as thallium germanate, germanium dioxide, dimethyltin maleate, dibutyltin oxide, hydroxybutyltin oxide, monobutyltin tris (2-
Tin compounds such as ethylhexanoate), and the like.
These can be used alone or in combination of two or more.

When the polycondensation of the copolymerized polyester resin is carried out, a stabilizer such as triphenyl phosphate, triethyl phosphate, phosphoric acid or the like, a matting agent such as titanium dioxide or the like is used in a range which does not impair the characteristics of the present invention. May be added.

Next, the laminate of the present invention and a method for producing the same will be described. That is, the laminate of the present invention is made of copper,
(A) of metal plate layer selected from iron, aluminum and tinplate
, An adhesive layer (B) composed of the above-mentioned copolymerized polyester resin and a PET film (or PET sheet) layer
(C) is present at least in this order. Here, PET film refers to JIS Z-0108
Refers to those with a thickness of 0.25 mm or less as described in
The PET sheet is a sheet having a thickness exceeding 0.25 mm.

The adhesive layer (B) comprising the copolymerized polyester resin of the present invention may be formed by any method, but the copolymerized polyester resin is dissolved in an organic solvent, and a PET film (or PET film) is formed. Sheet)
Then, a method of removing the solvent is preferable. Alternatively, an adhesive layer (B) can be formed by applying a solution of a copolymerized polyester resin to the metal plate layer (A) and removing the solvent.

The organic solvent used for forming the adhesive layer (B) is not particularly limited as long as it can dissolve the copolymerized polyester resin of the present invention. , Xylene and other aromatic solvents, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, chlorobenzene, dichlorobenzene and other chlorinated solvents, ethyl acetate, Ester solvents such as isophorone and γ-butyrolactone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexone; ether solvents such as diethyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran and 1,4-dioxane , Methanol, ethanol, n-propanol, isopropanol, n-butanol, etc. Alcohol solvents, n-
Examples include aliphatic hydrocarbon solvents such as butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane and nonane, and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. These can be used alone or in combination of two or more.

Next, a metal plate layer selected from copper, iron, aluminum and tinplate is arranged so as to be (A), an adhesive layer (B), and a PET film (or PET sheet) layer (C). Then, the laminate is formed by a conventionally known method such as heat sealing, roll bonding, and heat compression.

At this time, the preheating temperature of the adherend (usually a metal plate) when the adherends are bonded to each other via the adhesive layer (B) is preferably in the range of 100 to 220 ° C. , 150 ° C
It is more preferable that the temperature is in the range of -200 ° C. Preheating temperature
When the temperature is lower than 100 ° C., no matter how much the pressure is increased, a material having a high adhesive strength cannot be obtained. On the other hand, the preheating temperature
If the temperature exceeds 220 ° C., the layer of the PET film (or PET sheet) as the adherend is undesirably deformed or wrinkled. The bonding pressure is 0.2
It is preferably set to kg / cm ² or more, and more preferably set to 0.5 ~3kg / cm ^2. If the pressure at the time of bonding is less than 0.2 kg / cm ² , a material having high bonding strength cannot be obtained even if the preheating temperature is increased and the pressing time is increased. Further, it is preferable that the pressure bonding time at the time of bonding is 0.2 to 5 seconds. Crimping time
When the heating time is less than 0.2 seconds, a material having a high adhesive strength cannot be obtained even if the preheating temperature is increased. On the other hand, if the pressing time exceeds 5 seconds, there is no problem in the adhesive strength of the obtained laminate, but it is not preferable because the productivity is poor.

The copolymerized polyester resin of the present invention is made of PE
It has particularly good adhesion to T film (or PET sheet) and metal plate (copper, iron, aluminum, tinplate),
The material used for the adherend is not limited to this, and can be used as an adhesive for various plastics. Specifically, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, polycarbonate resins, polyarylate resins, polyester resins such as polybutylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polystyrene resins, It is suitably used as an adhesive for (meth) acrylic resin and the like. The shape of the adherend is a film, a sheet,
The shape is not limited to a plate shape, and may be a fibrous shape, a cylindrical shape, or any other shape.

The copolymerized polyester resin of the present invention can be used alone as an adhesive resin, but can also be used in combination with a curing agent such as an isocyanate resin, a phenol resin, a melamine resin, or an epoxy resin. . Depending on the use, it is also possible to mix a phosphorus-based compound other than the phosphorus-containing dicarboxylic acid compound represented by the formula in order to impart further flame retardancy. Further, conventionally known additives such as a filler, a stabilizer, a lubricant, an antistatic agent, and a foaming agent may be blended as long as the characteristics of the present invention are not impaired.

[0028]

Next, the present invention will be described specifically with reference to examples and comparative examples. In Examples and Comparative Examples, the characteristic values of the copolymerized polyester resin and the evaluation of the laminate were measured by the following methods. (a) Relative viscosity of copolymerized polyester resin 0.5 g / weight ratio of the copolymerized polyester resin in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 1/1)
Dissolved at a concentration of dl. Next, using an Ubbelohde viscometer, the time during which the solution and the solvent dropped in the capillary was measured, and the ratio was determined to obtain the relative viscosity. (b) Glass transition temperature of copolyester resin Differential scanning calorimeter (DS, manufactured by Seiko Instruments Inc.)
C-7) was measured at a heating rate of 20 ° C./min. (C) Content of phosphorus atom in copolymerized polyester resin First, composition analysis (molar fraction) of the copolymerized polyester resin was performed by using ¹ NMR (Lamdba 300WB, manufactured by JEOL Ltd.). Next, based on the results, the content of phosphorus atoms was determined by the following equation. Here, M _i represents the formula weight of i component residues constituting the copolyester resin, m _i denotes the mole fraction of i component. (d) Flame retardancy of copolymerized polyester resin Evaluated based on the vertical flammability test for thin materials described in UL Standard UL-94. The thickness of the material used was 500 μm. (e) Adhesive strength of laminate The adhesive strength was measured using “Autograph AGS 100” manufactured by Shimadzu Corporation. The sample width of the laminate used for the measurement was 10 mm, the peeling rate was 50 mm / min, the measurement temperature was 20 ° C. and
Performed at 60 ° C.

Example 1 43.2 g of terephthalic acid, 23.2 g of isophthalic acid, sebacic acid
76.8 g, HCA-IA 72.6 g, neopentyl glycol 72.8
g and ethylene glycol 43.4 g were charged into the reactor, and the inside of the system was replaced with nitrogen. Then, the reactor was stirred while stirring at 30 rpm.
Heat to 240 ° C to melt the contents.
After reaching 40 ° C., the esterification reaction was performed for 4 hours. Then, 4.4 g of a 2% by weight solution of zinc acetate in ethylene glycol as a catalyst was charged into the reactor, the pressure in the system was reduced to 0.5 hPa while increasing the temperature in the system to 280 ° C., and a polycondensation reaction was performed at 280 ° C. for 6 hours. At the time when the polycondensation reaction was completed, the system was returned to normal pressure while filling nitrogen into the system, discharged in a molten state into a sheet, cooled and solidified. The amount of the obtained copolyester resin was 267 g.

Example 2 A copolymerized polyester resin was obtained in the same manner as in Example 1 except that the polycondensation reaction time was changed to 3 hours. The weight of the obtained copolymerized polyester resin was 264 g.

Example 3 The raw materials were charged as follows: terephthalic acid 41.5 g, isophthalic acid 1
A copolymerized polyester resin was obtained in the same manner as in Example 1, except that 6.6 g, sebacic acid 60.6 g, HCA-IA 115.5 g, neopentyl glycol 72.8 g, and ethylene glycol 43.4 were used. The obtained copolymerized polyester resin has 290
g.

Example 4 The raw materials were charged with terephthalic acid (49.8 g) and isophthalic acid (4).
A copolymerized polyester resin was obtained in the same manner as in Example 1 except that 4.8 g, 76.8 g of sebacic acid, 16.5 g of HCA-IA, 72.8 g of neopentyl glycol and 43.4 g of ethylene glycol were used. The obtained copolyester resin is 2
39 g.

Example 5 The raw materials were charged with terephthalic acid 23.2 g and isophthalic acid 2
A copolymerized polyester resin was obtained in the same manner as in Example 1, except that 3.2 g, 101.0 g of sebacic acid, 72.6 g of HCA-IA, 72.8 g of neopentyl glycol and 43.4 g of ethylene glycol were used. The resulting copolyester resin is
It was 271 g.

Example 6 Starting materials were charged with 48.1 g of terephthalic acid and 4 parts of isophthalic acid.
A copolymerized polyester resin was obtained in the same manner as in Example 1, except that 8.1 g, 40.4 g of sebacic acid, 72.6 g of HCA-IA, 72.8 g of neopentyl glycol and 43.4 g of ethylene glycol were used. The obtained copolyester resin is 2
It was 60 g.

Comparative Example 1 A copolymerized polyester resin was obtained in the same manner as in Example 1 except that the polycondensation reaction time was changed to 1 hour. The amount of the obtained copolyester resin was 265 g.

Comparative Example 2 A copolymerized polyester resin was obtained in the same manner as in Example 1 except that the polycondensation reaction time was changed to 8 hours. The amount of the obtained copolyester resin was 266 g.

Comparative Example 3 The raw materials were charged with 61.4 g of terephthalic acid and 4 parts of isophthalic acid.
1.5 g, sebacic acid 76.8 g, neopentyl glycol 72.
A copolymerized polyester resin was obtained in the same manner as in Example 1 except that the amount was changed to 8 g and 43.4 g of ethylene glycol.
The amount of the obtained copolyester resin was 233 g.

Comparative Example 4 The raw materials were charged with 21.6 g of terephthalic acid and 1 part of isophthalic acid.
A copolymerized polyester resin was obtained in the same manner as in Example 1, except that 6.6 g, 111.1 g of sebacic acid, 72.6 g of HCA-IA, 72.8 g of neopentyl glycol and 43.4 g of ethylene glycol were used. The resulting copolyester resin is
273 g.

Comparative Example 5 The raw materials were charged with 330 g of HCA-IA and 8 parts of ethylene glycol 8.
A copolymerized polyester resin was obtained in the same manner as in Example 1 except that the amount was changed to 6.8 g. The weight of the obtained copolyester resin was 356 g.

Table 1 shows the physical property values of the obtained copolyester resin.

[0041]

[Table 1]

Examples 7 to 20 and Comparative Examples 6 to 10 The copolymerized polyester resins obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were mixed with a mixed solvent of toluene and methyl ethyl ketone (volume ratio 1/1). After dissolving to a concentration of 30% by weight, the solution was applied on a PET film having a thickness of 25 μm, and then the solvent was removed to form an adhesive layer having a thickness of 10 μm. Then
The PET film on which the adhesive layer was formed was placed so that the metal plate preheated to the temperature shown in Table 2 was in contact with the adhesive layer, and pressed by a sealer under the conditions shown in Table 2,
A laminate composed of PET film / adhesive layer composed of copolymerized polyester resin / metal plate was obtained.

Table 2 shows the adhesive strength of the obtained laminate.

[0044]

[Table 2]

[0045]

According to the present invention, excellent flame retardancy and
A copolyester resin having good adhesion to a metal plate and a PET film (or a PET sheet) can be obtained. Therefore, the copolyester resin of the present invention is used in the electrical, electronic, mechanical, food, construction, and automotive fields, specifically, in electric wire coatings, electric components such as flat cables, PCM paints, It can be particularly suitably used as an adhesive resin for packaging materials such as building materials, foods and pharmaceuticals.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A polyester resin comprising one or more kinds of dicarboxylic acid components and one or more kinds of glycol components, wherein a phosphorus-containing dicarboxylic acid compound represented by the following formula is copolymerized. A copolymerized polyester resin for a flame-retardant adhesive, characterized by having a phosphorus atom content in the range of 0.05 to 5% by weight, a glass transition temperature of -30 to 40 ° C and a relative viscosity of 1.1 to 1.6. . Embedded image 2. A metal plate layer selected from copper, iron, aluminum and tinplate (A), an adhesive layer (B) comprising a flame-retardant copolymerized polyester resin according to claim 1, and a PET film (or A laminate (PET sheet) at least in this order.