JP2014074140A - Low boiling-point solvent soluble resin, and ink material and ink using the same - Google Patents

Abstract

An object of the present invention is to provide a low-boiling-point solvent-soluble resin that is excellent in heat resistance and can be used as a printing ink composition, and an ink material and ink using the resin.
SOLUTION: A polyamide-imide resin synthesized from trimellitic acid chloride and an ortho-positioned alkylated methylenebisaniline in which R1 to R4 are alkyl groups having 1 to 3 carbon atoms, and the ortho-positioned alkylated methylenebisaniline. Of 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2-isopropyl-6-methylaniline), 4,4′-methylenebis (2,6-diisopropylaniline) It is possible to provide an ink material and an ink characterized by adding any low-boiling-point solvent-soluble resin and an organic solvent soluble in the resin.
[Selection figure] None

Description

  The present invention relates to a low-boiling-point solvent-soluble resin, an ink material using the resin, and an ink.

  In general, in a flexible printed circuit board, in order to protect a circuit, a cover lay film in which an adhesive is applied to a plastic film such as a polyimide film or a polyester film has been covered. However, the cover lay film has a complicated circuit because the part to be exposed of the circuit is punched or drilled, and then overlaid while being aligned on the circuit board and bonded together by heat and pressure. Then, it was difficult to drill and position the coverlay film. In addition, since the adhesive used for the coverlay film has poor heat resistance and insulation reliability, these characteristics as a circuit board are inevitably poor.

  In order to solve this problem, a so-called printing method in which a printing ink composition is applied to the substrate surface has been developed and widely used. For example, Patent Document 1 discloses an ink composition containing an epoxy resin having two or more epoxy groups in a soluble polyimide molecule having a repeating unit, a curing agent, a solvent, and a thixotropic agent. Recently, the environmental characteristics required for substrates have become increasingly severe, and high heat resistance has been demanded.

  However, in Patent Document 1, when 40 parts by weight of the epoxy resin described in the examples is added, although there is a short-time heat resistance such as solder heat resistance, long-time heat resistance, for example, 200 ° C., 100 In terms of time, it can be easily estimated that physical properties will deteriorate due to deterioration. There is a need to provide ink in which a resin that does not have sufficient heat resistance and that satisfies the required heat resistance requirements is dissolved.

  It is the thing of patent document 2 which solves the subject which concerns, it is excellent in heat resistance, for example, it can also be used as a printing ink composition suitable also as a protective covering material of the circuit of a flexible printed circuit board, Ink materials and inks that are soluble in low-boiling solvents and have heat resistance are provided.

  To date, polyamideimide resins that are soluble in low-boiling solvents have already been reported. For example, Patent Document 3 describes a polyamideimide resin that is soluble in a low hygroscopic and low boiling point solvent.

Japanese Patent Laid-Open No. 11-172181 JP 2012-7069 A JP 2002-275263 A

  However, the solvent that is soluble in the resin (ink material) described in Cited Document 2 is 100 ° C. or higher even at the lowest boiling point. Recently, the market demand has become more advanced and it is desired to use a low-boiling solvent. Specifically, a resin that dissolves in a general-purpose solvent such as methyl ethyl ketone (boiling point 79.5 degrees C.) is desired. It is rare.

  Furthermore, the polyamideimide resin of Patent Document 3 is difficult to polymerize because it uses a diisocyanate or diamine having an alicyclic structure as a raw material, and since the heat resistance is low only with an alicyclic structure, it is a resin with a highly heat-resistant aromatic structure. A part of the structure must be denatured, and the synthesis system becomes complicated.

  The present invention has been made in view of such a problem, and is particularly soluble in a low-boiling solvent at 100 ° C. or lower while being excellent in heat resistance, a low-boiling solvent-soluble resin, and heat resistance using the resin It is an object of the present invention to provide an ink material and ink having properties.

As a means for solving this problem, for example, an embodiment of the present invention according to the present invention has the following configuration.
That is, a low-boiling solvent characterized by being a polyamideimide synthesized from trimellitic acid chloride (hereinafter referred to as TAC) and an ortho-alkylated methylenebisaniline in which R1 to R4 are alkyl groups having 1 to 3 carbon atoms A soluble resin is used.

For example, the ortho-alkylated methylenebisaniline includes 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2-isopropyl-6-methylaniline), 4,4 ′. -Methylenebis (2,6-diisopropylaniline).
Or it is set as the ink raw material which added the organic solvent which can be melt | dissolved in the said low boiling-point solvent soluble resin.

  The soluble organic solvent includes 1-methyl-2-pyrrolidone, dihydrofuran-2 (3H) -one, 1,2-bis (methoxyethoxy) ethane, bis (2-methoxyethyl) ether, cyclohexanone , Cyclopentanone, butyl acetate, tetrahydrofuran, 2-butanone, or 2-propanone.

Alternatively, an ink material characterized in that an organic solvent that can be dissolved in a low-boiling-point solvent-soluble resin is characterized by comprising the following structural formula.

  Alternatively, the ink material may be an ink obtained by adding a desired pigment, dye, or a mixture thereof to the ink material described above.

  According to the present invention, there is provided a low-boiling-point solvent-soluble resin that is soluble in a low-boiling-point solvent of 100 ° C. or less while having excellent heat resistance, and a heat-resistant ink material and ink using the resin. Can be provided.

  Hereinafter, an embodiment of an invention according to the present invention will be described in detail. In this embodiment, a heat resistance, sufficient mechanical strength, a low-boiling-point solvent-soluble resin, a heat-resistant ink material using the resin, and a heat-resistant ink will be described.

[Outline of Embodiment]
In this embodiment, trimellitic acid chloride (hereinafter “TAC”, structural formula A) and ortho-alkylated methylenebisaniline (structural formula B) in which R1 to R4 are alkyl groups having 1 to 3 carbon atoms are used. Was used as a raw material to synthesize a polyamideimide resin (structural formula C).

Structural formula A TAC

Structural Formula B Ortho-Polyalkylated Methylene Bisaniline

Structural formula C Polyamideimide resin

Thereby, it became possible to dissolve in a low boiling point solvent having a market demand (for example, methyl ethyl ketone having a boiling point of 79.5 ° C.).
The ortho-positioned alkylated methylenebisaniline of the structural formula B includes 4,4′-methylenebis (2,6-diethylaniline) (hereinafter “M-DEA”, structural formula 1 ′), 4,4′-methylenebis (2 -Isopropyl-6-methylaniline) (hereinafter “M-MIPA”, structural formula 2 ′, 4,4′-methylenebis (2,6-diisopropylaniline) (hereinafter “M-DIPA”, structural formula 3 ′) The developed products are 1, 2, and 3, respectively.

構造式 1’ M-DEA

Structural formula 1 'M-DEA

構造式 2’ M-MIPA

Structural formula 2 'M-MIPA

構造式 3’ M-DIPA

Structural formula 3 'M-DIPA

As a result of evaluating the resin, it was found that the resin is soluble in various solvents including a low boiling point solvent.
Further, as will be described in detail later, the glass transition temperatures of the developed products 1, 2, and 3 were 260, 279, and 282 ° C., respectively, and it was confirmed that they had high heat resistance.

  Furthermore, an ink material can be produced by adding an organic solvent that can be dissolved in this type of resin. For example, an ink can be produced by adding a desired pigment or dye (or a mixture thereof) to the ink material. The types of pigments and dyes added to the ink material are not particularly limited and can be appropriately selected.

[Synthesis of the developed product 1]
A method for synthesizing the developed product 1 of this embodiment will be described below.
First, 187.54 g (0.604 mol) of M-DEA, 61.12 g (0.604 mol) of triethylamine, and 800 g of dimethylacetamide were added to a 2 L separable flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, and stirred uniformly. It was set as the solution. While cooling this solution, 127.18 g (0.604 mol) of trimellitic anhydride chloride was slowly added. After completion of the addition, cooling was stopped and the mixture was stirred at room temperature. When the increase in viscosity was finished, 0.56 g (0.006 mol) of aniline was added and stirred for 1 hour.

Subsequently, 120 ml of acetic anhydride and 61 ml of pyridine were added to this solution, and the mixture was stirred at 55 ° C. for 2 hours for imidization.
The obtained reaction solution was added to a water / methanol mixed solution, and the obtained powder was washed with water and dried to obtain a polyamideimide powder (developed product 1).

[Synthesis of developed product 2]
It carried out on the same conditions except having used 187.54g (0.604 mol) of M-MIPA instead of M-DEA in the synthesis | combination of the above-mentioned development product 1.
[Synthesis of the developed product 3]
The synthesis of the developed product 1 was performed under the same conditions except that M-DIPA 221.43 g (0.604 mol) was used instead of M-DEA and 896 g of dimethylacetamide was used.

[Synthesis of Comparative Product 1]
In place of M-DEA of the developed product 1 described above, bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter “BAPS-M, structural formula 4 ′)” was used, and the method described in Patent Document 2 was used. And synthesized.

構造式 4’ BAPS-M

Structural formula 4 'BAPS-M

〔Evaluation of the physical properties〕
Molecular weight measurement
3 mg of the resulting polyamideimide powder was dissolved in 3 mL of LiBr-added DMF and filtered through a 0.45 μm hydrophilic PTFE membrane filter cartridge (Millex-LH, manufactured by Nihon Millipore). Chromatography was used to measure molecular weight. The measurement conditions are as follows.

Column: TSKgel Super AWM-H 60 mm (ID) x 150 mm (L)
(Tosoh)
Mobile phase: DFM 10 mM L LiBr added Flow rate: 0.6 mL / min
Detector: RI-101 differential refractometer (manufactured by Showa Denko)
Injection volume: 20 μL
Molecular weight calibration: monodisperse polystyrene

なお、以下、表１の分子量の少ない開発品を「開発品１」分子量の多い開発品を「開発品１−２」と称する。 The measurement results are shown in the table below.

Hereinafter, the developed product having a low molecular weight in Table 1 is referred to as “developed product 1”, and the developed product having a large molecular weight is referred to as “developed product 1-2”.

[Solubility]
The developed polyamideimide powder was added to the organic solvent shown below so as to be 20 wt%, and the solubility was confirmed. There was no insoluble matter and it was determined that there was solubility by visually confirming that it was fluid. Moreover, the time-dependent change of the prepared solution was also observed.

1-methyl-2-pyrrolidone (hereinafter “NMP”)
Dihydrofuran-2 (3H) -one (hereinafter “GBL”)
1,2-bis (methoxyethoxy) ethane (hereinafter “TG”)
Bis (2-methoxyethyl) ether (hereinafter “DG”)
Cyclohexanone (hereinafter “CH”)
Cyclopentanone (hereinafter “CP”)
Butyl acetate tetrahydrofuran (hereinafter “THF”)
2-butanone (hereinafter “MEK”)
2-propanone (hereinafter referred to as “acetone”)

※1 ○ 表記のものは少なくとも1 日は外観に変化がないことを確認。
※2 △ 表記のものは溶解してはいるが、溶液が分離し均一溶液ではない。

* 1 ○ Confirmed that there is no change in appearance for at least one day.
* 2 The products marked with △ are dissolved, but the solution is separated and is not a homogeneous solution.

General organic solvent-soluble polyamideimide is soluble only in NMP, but the developed product is soluble in many solvents other than NMP, and is also used in MEK, THF, etc., which are low boiling point solvents below 100 ° C. Dissolve.
NMP has a boiling point as high as 202 ° C., and drying requires long-time heating at a high temperature, so that productivity is poor and expensive equipment corresponding to the high temperature is also required.
Since the developed product can use a solvent other than NMP, it can be easily coated and dried to form a polyamideimide film.

  As shown in Tables 2 and 3, since a solvent other than NMP that does not have the above disadvantages can be used, it is possible to make an ink that can be easily screen-printed and can be dried at a low temperature. Use as a lay ink can be expected. When used as an ink for screen printing or the like, it can be used by being dissolved in various solvents, and an ink material that can be printed and dried more easily than a general product to form a polyamideimide film can be provided.

[Other physical properties]
Measurement method Tensile strength, elastic modulus, elongation rate NMP ink of the developed products 1 to 3 is applied on a glass that has been subjected to a release treatment with a blade coater and dried to produce a 25 μm thick film for measurement. It was.
The apparatus used was STRROGRAPH E-L (manufactured by Toyo Seiki Seisakusho). The measurement conditions are as follows.
Sample size: 10mm x 130mm
Tensile speed: 100 mm / min

Glass transition temperature, coefficient of thermal expansion A film having a thickness of 25 μm was prepared by the same procedure as described above and used for measurement.
As a device, Thermo Plus TMA8310 (manufactured by Rigaku) was used.
The measurement conditions are as follows.
Sample size: 5mm x 15mm
Measurement method: TMA method Measurement range: Room temperature to 300 ° C
Temperature increase rate: 10 ° C / min

表４から明かなように本実施の形態例開発品によれば、ポリアミドイミド樹脂が本来持つ高いガラス転移温度を有する耐熱性の高い樹脂を溶解したインクが提供できる。 Results The measurement results are shown in the table below.

As apparent from Table 4, according to the developed product of the present embodiment, it is possible to provide an ink in which a highly heat-resistant resin having a high glass transition temperature inherent to a polyamide-imide resin is dissolved.

  As described above, according to the developed product of this embodiment, a polyamide-imide resin that is soluble in various solvents including a low-boiling solvent can be provided.

Application example of this embodiment Example of use as a low-temperature dry coverlay ink The use of a low-boiling solvent enables easy screen-printing ink that can be dried at low temperatures. Use as an ink can be expected.

・ Example of use as heat-resistant coating resin Application example of this embodiment ・ Application example of low-temperature dry coverlay ink
Since a resin that can be dissolved in a low-boiling solvent such as MEK can be provided, it can be used as an epoxy additive.
Moreover, since it dissolves in a low-boiling solvent, it is possible to form a heat-resistant film at a location where a high-boiling solvent cannot be used.

Claims (6)

  A low-boiling solvent-soluble resin characterized by being a polyamideimide synthesized from trimellitic acid chloride and an ortho-positioned alkylated methylenebisaniline in which R1 to R4 are alkyl groups having 1 to 3 carbon atoms. Examples of the ortho-alkylated methylenebisaniline include 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2-isopropyl-6-methylaniline), 4,4′-methylenebis ( 2. The low-boiling-point solvent-soluble resin according to claim 1, which is any one of 2,6-diisopropylaniline). An ink material, wherein an organic solvent that is soluble in the low-boiling-point solvent-soluble resin according to claim 1 is added. Examples of the soluble organic solvent include 1-methyl-2-pyrrolidone, dihydrofuran-2 (3H) -one, 1,2-bis (methoxyethoxy) ethane, bis (2-methoxyethyl) ether, cyclohexanone, cyclohexane The ink material according to claim 3, wherein any one of pentanone, butyl acetate, tetrahydrofuran, 2-butanone, and 2-propanone is contained. An ink material comprising an organic solvent that is soluble in a low-boiling-point solvent-soluble resin, characterized by comprising the following structural formula:

6. An ink comprising a desired pigment, dye or a mixture thereof added to the ink material according to claim 3.