KR20170135273A - Method for manufacturing water-soluble polyurethane/epoxy hybrid resin for speaker damper - Google Patents

Abstract

The present invention relates to a water-based polyurethane / epoxy hybrid resin for a speaker damper having excellent properties such as processability, flexibility, toughness and chemical resistance as well as being environmentally friendly by mixing an aqueous polyurethane having high impact strength and excellent elasticity and an epoxy resin as a thermosetting resin And a method for producing the same.
The present invention relates to a process for producing polyurethane, which comprises a first step of reacting an ester polyol, an ether polyol or a carbonate polyol together with an aromatic diisocyanate and a glycol having a weight average molecular weight of 60 to 200 to synthesize polyurethane and emulsifying the polyurethane with water, A second step of mixing and stirring the resins with each other to prepare a hybrid resin, and a third step of adding an amine-based, amide-based or acid anhydride-based curing agent and an epoxy reaction promoter to the hybrid resin and curing the mixture .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a water-soluble polyurethane / epoxy hybrid resin for speaker damper,

The present invention relates to a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper, and more particularly to a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper by mixing an aqueous polyurethane having high impact strength and excellent elasticity and an epoxy resin as a thermosetting resin, To an aqueous polyurethane / epoxy hybrid resin for speaker damper having excellent physical properties such as flexibility, toughness and chemical resistance.

In general, a speaker is an output converter that converts amplified electric vibration from an amplifier into mechanical vibration, and converts the electrical signal into a sound signal.

The principle of this speaker is to send a current to the voice coil inside the permanent magnet, to move the coil back and forth according to the direction of the current, to attach a circular plate at the end, and to move the plate back and forth.

Among them, the damper which affects the speaker sound drive and high output plays a role of determining the voice coil position in the speaker, and it supports the voice coil together with the neck portion of the cone paper so as to accurately move up and down It is an element that prevents excessive motion and determines the output together with the magnet.

2. Description of the Related Art In recent years, the performance of automotive speakers and speakers for audiovisual machines has been improved and upgraded. As a result, the role of the damper, which affects the sound quality of speakers, has become very important. In particular, a vehicle speaker needs to have a plurality of loudspeakers installed therein and each loudspeaker plays a role for each loudspeaker. In the case of a loudspeaker, a difference between a high output and a loudness must be large. Therefore, A product that can exhibit the largest value within the market is required.

On the other hand, the dampers are applied to the molding technology after impregnation with phenol in the 1970s ~ 1980s introduced from Japan, and the dampers are coated with phenol resin to make woven with cotton or hemp, . At this time, the factors controlling the elasticity of the damper include the physical properties of the coating material, the size and number of wrinkles, and the overall width.

The dampers thus manufactured have a low manufacturing cost, excellent workability, moldability, and physical properties because they use phenol resin having a low unit price. However, due to the flexibility and elasticity of the dampers applied to the speaker dampers, When used for more than 10 hours, the crack (crack) occurs and the tearing phenomenon causes the coated phenol resin to be dropped, which adversely affects the sound quality.

In addition, phenolic resins are produced by the addition condensation of phenol and formaldehyde, which are carcinogenic substances designated as hazardous substances in 84 countries including Europe. As interest in environmentally friendly materials and government regulations are intensifying, The need for

Accordingly, it is urgent to develop a coating resin for use in a speaker damper which has excellent physical properties such as workability, flexibility, toughness and chemical resistance, and is environmentally friendly as well as excellent in elastic recovery and can provide high quality sound.

Korean Patent Registration No. 10-0836778 (June 03, 2008) Korean Registered Patent No. 10-1503147 (Mar. 10, 2015)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is therefore an object of the present invention to provide a polyolefin resin composition which is excellent in flexibility, elasticity, toughness and chemical resistance And an object of the present invention is to provide a method for manufacturing a water-based polyurethane / epoxy hybrid resin for a speaker damper which has physical properties and is environment-friendly.

It is another object of the present invention to provide a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper which is harmless to the human body by using a material made of an environmentally friendly material.

Meanwhile, the object of the present invention is not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood from the following description.

To achieve the above object, the present invention provides a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper, comprising reacting an ether polyol and a carbonate polyol together with an aromatic diisocyanate and a glycol having a weight average molecular weight of 60 to 200 A first step of synthesizing a polyurethane and emulsifying the polyurethane with water, a second step of mixing and stirring the polyurethane and the epoxy resin with each other to produce a hybrid resin, and a second step of adding an amine-based, amide-based or acid anhydride- And a third step of curing by adding an epoxy reaction promoter.

Preferably, in the first step, 20 to 40 parts by weight of the polyol, 5 to 15 parts by weight of the aromatic diisocyanate, and 3 to 10 parts by weight of the glycol having a weight average molecular weight of 60 to 200, By weight.

Preferably, the polyol is a mixture of polycarbonatediol (PCD) and polytetramethylene glycol (PTMG).

Preferably, the aromatic diisocyanate is a mixture of toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI).

Preferably, an additive including an antioxidant, a UV stabilizer and an emulsifier is further added, and the content of the additive is 0.2 to 2.0 parts by weight based on 50 to 60 parts by weight of the water.

Preferably, the polyurethane is characterized in that it is produced at 50 to 90 DEG C for 10 to 15 hours.

Preferably, in the second step, 20 parts by weight of the epoxy resin is added to 100 parts by weight of the polyurethane.

Preferably, in the second step, the content of the crosslinking agent is 60 to 70 phr with respect to the epoxy resin, and the hybrid resin is produced at 10 to 35 ° C for 1 to 3 hours.

Preferably, in the third step, the content of the curing agent is 60 to 70 phr with respect to the epoxy resin, and the content of the epoxy reaction promoter is 0.5 to 2.0 phr with respect to the epoxy resin.

Preferably, in the third step, the hybrid resin is cured at 130 to 150 DEG C for 3 to 5 minutes.

The method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper according to the present invention has an environment-friendly effect by using polyurethane produced by using water as a solvent.

By mixing the epoxy resin with the water-based polyurethane, it not only has flexibility, elasticity and toughness, which are characteristics of the polyurethane, but also has a property of low shrinkage when cured, which is an epoxy resin, and flame retardancy, There is an effect that can be done.

1 is a flow chart showing a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper according to an embodiment of the present invention.
2A to 2C are photographs showing a polyurethane synthesized for each polyol according to an embodiment of the present invention.
3 is a photograph showing a polyurethane synthesized by diisocyanate and diol according to an embodiment of the present invention.
4A and 4B are photographs showing a hybrid resin synthesized by kind and content of an epoxy resin according to an embodiment of the present invention.
FIG. 5 is a photograph showing a test of the bending resistance of a fabric coated with a hybrid resin according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below, but may be embodied in various different forms, and these embodiments are not intended to be exhaustive or to limit the scope of the present invention to the precise form disclosed, It is provided to inform the person completely of the scope of the invention. And the terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. The singular forms herein include plural forms unless the context clearly dictates otherwise.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Brief Description of Drawings FIG. 1 is a block diagram of a computer system according to an embodiment of the present invention; FIG. 2 is a block diagram of a computer system according to an embodiment of the present invention; FIG.

As shown in FIG. 1, a method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper according to an embodiment of the present invention includes a first step (S100) of producing a polyurethane, a second step (S200) for curing the hybrid resin and a third step (S300) for curing the hybrid resin.

First, in a first step S100, an ether polyol and a carbonate polyol are reacted together with an aromatic diisocyanate and a glycol having a weight average molecular weight of 60 to 200 to synthesize a polyurethane, followed by emulsification with water.

The polyol is an active hydrogen compound used for producing a polyurethane by reacting with an isocyanate (-NCO) to be described later and having two or more active hydrogen groups such as a hydroxyl group and an amine group in the molecule.

Glycol is used as a chain extender, reactive emulsifier, and polymer polyol reacts with isocyanate and is used in polyurethane production. The polymer polyol includes a polyester polyol, a polyether polyol, a polycarbonate polyol and the like.

Specifically, polyether polyols, polyester polyols, carbonate polyols, and caprolactone polyols are widely used as the types of polyols.

First, the polyether polyol is produced by mixing ethylene oxide with propylene oxide and is excellent in ozone resistance and abrasion resistance, and is used in mattresses for automobile tires and bedding.

The polycarbonate polyol has -OH groups at both ends and a carbonate bond in the main chain and is excellent in heat resistance, durability, abrasion resistance, mechanical properties, water resistance and weather resistance and is used in elastomers, synthetic leather, paints and the like.

The polyester polyol is classified into a polyester polyol synthesized by polycondensation with an acid and a hydroxyl compound and a polymerization unit such as a caprolactone monomer. The condensation polyester polyol includes a -OH group such as dicarboxylic acid and glycol And has a molecular weight of 500 to 4000 having terminal primary -OH groups. The weight-added polyester polyol is obtained by reacting a lactone or a derivative thereof with a small amount of a diol, triol or amine as a initiator.

In the present invention, the polyol is a mixture of polycarbonate diol (PCD), one of the polycarbonate polyols, and polytetramethylene glycol (PTMG), which is one of the polyether polyols.

Further, the polycarbonate diol has excellent water resistance, heat resistance and mechanical properties, and can have a weight average molecular weight of 500 to 3,000, particularly 1,000 to 2,000. The final polyurethane consists of a hard segment imparted from the glycol and isocyanate and a soft segment imparted from the polyol. When the weight average molecular weight of the polycarbonate diol is less than 1,000, the hardness of the final polyurethane When the weight average molecular weight of the polycarbonate diol is more than 2,000, the content of the hard portion of the final polyurethane is very low, so that the low hardness and the mechanical strength can be improved. There is a problem.

At this time, it is possible to further add a polyester polyol as the polyol. Polyester polyols can be used together with polycarbonate diols to compensate for the disadvantages of polycarbonate diols, which have rather poor mechanical properties due to their excellent heat resistance and mechanical properties. They can be used in combination with hardness, strength, flexibility and elasticity of the final polyurethane Weight average molecular weight of 500 to 4,000, especially 1,000 to 2,000.

Since polytetramethylene glycol has excellent cold resistance, water resistance, heat resistance and mechanical properties, polyester polyol and polycarbonate diol can be used together with polyester polyol and polycarbonate diol in order to compensate for shortcomings of polyester polyol and polycarbonate diol, In consideration of the hardness, strength, flexibility, elasticity and the like of the final polyurethane, the weight average molecular weight may be 500 to 3,000, particularly 1,000 to 2,000.

On the other hand, a diisocyanate is a compound containing two -NCO (isocyanate) groups, and has a toughness and a high reactivity, and reacts with a compound having an active hydrogen to form various bonds.

In the present invention, an aromatic diisocyanate is used to satisfy various physical properties such as flexural strength, tensile strength, elasticity and the like. In particular, toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI) use.

The glycols used as the chain extender and emulsifier are those having a weight average molecular weight of 60 to 200.

At this time, there are no glycols having a weight average molecular weight of less than 60. When the weight average molecular weight is more than 200, the content of the hard portion is very low, resulting in softness, resulting in low hardness and mechanical strength.

Specifically, the first step (S100) comprises 20 to 40 parts by weight of polyol, 5 to 15 parts by weight of aromatic diisocyanate, and 3 to 10 parts by weight of glycols having a weight average molecular weight of 60 to 200, based on 50 to 60 parts by weight of water.

In this case, water is added to emulsify polyurethane. When the amount is less than 50 parts by weight, viscosity increases and penetration into the fabric is difficult. When the amount is more than 60 parts by weight, viscosity is low, .

When the content of the polyol is less than 20 parts by weight, the hard part content of the final polyurethane is somewhat increased, and the water resistance is lowered, and the tensile strength and 100% modulus are increased and the flexibility is lowered. If the content of the polyol is more than 40 parts by weight, the soft portion content of the final polyurethane becomes somewhat higher, so that the tensile strength and 100% modulus are lowered, so there is a fear that the abrasion strength and heat resistance are lowered and the elasticity is lowered due to excessive flexibility . In this case, the 100% modulus refers to the modulus of elasticity that represents the ratio of stress to strain, and in the case of fiber, it refers to the modulus of elasticity against tensile, which indicates the hardness and the year of the material.

When the amount of the aromatic diisocyanate is less than 5 parts by weight, synthesis of the final polyurethane is not sufficiently achieved. When the amount of the aromatic diisocyanate exceeds 15 parts by weight, the aromatic diisocyanate remaining in the synthesis reaction of the final polyurethane is excessively The water is reacted with water to cause a problem of flexibility and a change over time.

If the content of glycols having a weight average molecular weight of 60 to 200 is less than 3 parts by weight, the tensile strength and 100% modulus may be lowered, and the abrasion strength and heat resistance may be lowered, and the elasticity may be deteriorated due to excessive flexibility. When the content of the diol having a weight average molecular weight of 60 to 200 exceeds 5 parts by weight, the tensile strength and 100% modulus are increased and the flexibility is lowered.

In addition, in the first step (S100), an additive including an antioxidant, a UV stabilizer and an emulsifier may be further added.

At this time, the antioxidant has an effect of preventing polyurethane from being oxidized by heat and breaking the chain, and the UV stabilizer has an effect of preventing the chain of the polyurethane from being broken by ultraviolet rays. The emulsifier is water and poly There is an effect that the organism used for urethane production can be stably mixed.

Specifically, the content of the additive is 0.2 to 2.0 parts by weight based on 50 to 60 parts by weight of water.

When the content of the antioxidant is less than 0.2 parts by weight, the chain of polyurethane is broken by heat and the coloring and water resistance are deteriorated. When the amount of the antioxidant is more than 2.0 parts by weight, There is a problem in that although the discoloration prevention effect is exhibited, the manufacturing cost is increased and the physical properties are lowered.

When the content of the UV stabilizer is less than 0.2 parts by weight, there is a risk of discoloration due to chain breakage due to ultraviolet rays. When the content is more than 2.0 parts by weight, a discoloration preventing effect similar to that in the case of using a weight part within the above- There is a problem that the manufacturing cost increases and migration occurs. At this time, migration refers to migration of dyes from polyurethane when a substance comes in contact with the polyurethane subjected to the dyeing process.

When the content of the emulsifier is less than 0.2 part by weight, there is a problem that the water used as the solvent and the organism used for producing the polyurethane are not stably mixed. When the amount is more than 2.0 parts by weight, There is a problem that the manufacturing cost is increased and the physical properties are lowered.

In addition, the first step (SlOO) may be performed at 50 to 90 DEG C for 10 to 15 hours. When the temperature is lower than 50 ° C, the reaction rate is slow, unreacted materials are generated, and physical properties such as elasticity and heat resistance are lowered. When the temperature is higher than 90 ° C, the reaction rate is increased and viscosity of the reactant is difficult to control. There is a fear of deterioration of physical properties.

Further, the RPM can be 60 to 90 when the ether polyol and the carbonate polyol are reacted with the aromatic diisocyanate and the glycols having a weight average molecular weight of 60 to 200 to synthesize the polyurethane. In the case of less than RPM 60 It may be difficult to produce a compound having homogeneous physical properties. If the RPM is more than 90, the reaction rate may be increased and it may be difficult to control the viscosity of the reactant.

When the synthesized polyurethane is emulsified with water, the RPM may be 200 to 400. When the RPM is less than 200, the particle size is increased. When the RPM is more than 400, the particle size is too small and the viscosity is lowered. have.

Next, referring to the second step (S200), a polyurethane and an epoxy resin are mixed with each other and stirred to prepare a hybrid resin.

Here, the epoxy resin is used for heat resistance and hardness which are difficult to be expressed in polyurethane, and it is preferable to use a bis-phenol A based epoxy resin.

When 20 parts by weight of the epoxy resin is mixed with 100 parts by weight of the polyurethane, the final polyurethane can have appropriate heat resistance, hardness and elasticity and can prevent the weather resistance from deteriorating. If it exceeds 20 parts by weight, The elasticity and the bending property (the property that the object can be easily bent and recovered without being destroyed) deteriorate.

In addition, the cross-linking agent is added in order to cross-link the linear polymer molecules to produce a polymer compound having a three-dimensional network structure.

Specifically, the content of the crosslinking agent is 60 to 70 phr with respect to the epoxy resin. When the content of the crosslinking agent is less than 60 phr, there is a problem that the reaction between the polyurethane and the epoxy resin does not sufficiently take place because the crosslinking agent is not sufficiently crosslinked. When the content of the crosslinking agent exceeds 70 phr, the intermolecular crosslinking degree increases and the hardness becomes excessively high. There is a problem in that the flexibility (property that the object can be easily bent and recovered without being destroyed) is lowered.

The second step S200 may be performed at 10 to 35 DEG C for 1 to 3 hours. If the temperature is lower than 10 ° C, water used as a solvent may be frozen. If the temperature is higher than 35 ° C, a cohesive force is generated in a liquid phase hybrid resin and storage stability is deteriorated. When the reaction time is less than 1 hour, the stirring is not performed well and it is difficult to produce a homogeneous hybrid resin. When the reaction time exceeds 3 hours, there is a problem that storage stability is deteriorated due to generation of heat and agglomeration due to agitation for a long time.

Finally, in a third step (S300), an amine-based, amide-based or acid anhydride-based curing agent and an epoxy reaction promoter are added to the hybrid resin and cured.

Here, the curing agent is used for strengthening polymerization or intermolecular bonding, and may be selected from amine series, amide series or acid anhydride series in consideration of pot life and curing conditions.

The content of such a curing agent is preferably 60 to 70 phr with respect to the epoxy resin. If it is less than 60 phr, it may not be sufficiently cured and physical properties may be deteriorated. If it exceeds 70 phr, it may affect the physical properties after processing due to the influence of the remaining curing agent.

Also, the epoxy reaction promoter is added for a better reaction than when curing the hybrid resin. In the present invention, it is preferable to use amine series, and when the epoxy reaction promoter is not added, the reaction rate is very slow.

The content of such an epoxy reaction promoter is preferably 0.5 to 2.0 phr with respect to the epoxy resin. When the amount is less than 0.5 phr, the completion time of the curing of the hybrid resin is slowed. When the amount exceeds 2.0 phr, the effect is similar to that when the weight part is used within the above range, but there is a fear of side reaction due to an excessive amount of the epoxy reaction promoter There is a problem that the physical properties are deteriorated.

Further, the third step (S300) may be performed at 130 to 150 DEG C for 3 to 5 minutes. If the temperature is lower than 130 ° C, the hybrid resin may not be cured sufficiently, and if it is higher than 150 ° C, side reactions may occur.

If the reaction time is less than 3 minutes, the hybrid resin may not be synthesized sufficiently. If the reaction time is more than 5 minutes, side reaction may occur.

Hereinafter, the present invention will be described in more detail with reference to the following experimental examples.

<Experimental Example 1_ Comparison of Physical Properties of Polyurethane Prepared by Polyol>

In this Experimental Example 1, to select the soft portion occupying the largest percentage of polyurethane, urethane was prepared for each type of polyol, and then dried.

The reason for checking the surface condition after drying the polyurethane is that when the crack (crack) occurs on the surface after impregnating the fabric of the speaker damper, durability and sound quality may be deteriorated due to the vibration of the speaker damper.

division
Furtherance
Solids
(%) Viscosity
(cps / 25 &lt; 0 &gt; C) after drying
Surface condition
(110 DEG C, 60 min) EPUD-1001-1 PTMG / IPDI / DMBA 45 4,000 crack EPUD-1001-2 PPG / IPDI / DMBA 45 3,500 clear EPUD-1001-3 Esterdiol (1) / IPDI / DMBA 45 2,000 crack EPUD-1001-4 Esterdiol (2) / IPDI / DMBA 45 2,500 crack EPUD-1001-5 Esterdiol (3) / IPDI / DMBA 45 3,000 crack EPUD-1001-6 Esterdiol (4) / IPDI / DMBA 45 2,400 clear EPUD-1001-7 Esterdiol (5) / IPDI / DMBA 45 3,500 clear EPUD-1001-8 PCD (HOMO) / IPDI / DMBA 45 3,800 crack EPUD-1001-9 PCD (COPOLYMER) / IPDI / DMBA 45 2,600 clear EPUD-1001-10 PTMG / Esterdiol (1)
/ IPDI / DMBA 45 2,700 crack EPUD-1001-11 PTMG / Esterdiol (2) /
IPDI / DMBA 45 3,500 crack EPUD-1001-12 PTMG / PCD (COPOLYMER)
/ IPDI / DMBA 45 3,000 clear EPUD-1001-13 Esterdiol (1) / Esterdiol (2) / IPDI / DMBA 45 3,700 crack EPUD-1001-14 Esterdiol (1) / Esterdiol (3)
/ IPDI / DMBA 45 3,900 crack EPUD-1001-15 Esterdiol (1) / Esterdiol (5)
/ IPDI / DMBA 45 3,600 clear EPUD-1001-16 PCD (COPOLYMER)
/ Esterdiol (3) / IPDI / DMBA 45 2,200 crack EPUD-1001-17 PCD (COPOLYMER) / Esterdiol (4) / IPDI / DMBA 45 3,100 clear

Esterdiol (1): Poly (1,4-buthanediol adipate)

Esterdiol (2): Poly (methylene adipate)

Esterdiol (3): Poly (1,6-hexanediol adipate)

Esterdiol (4): Poly (3-methyl 1,5-pentanediol adipate)

Esterdiol (5): Poly (neopenthyl glycol adipate)

DMBA: Dimethyl butyric acid

The specific composition including DMBA as an emulsifier was as shown in Table 1, and the other raw materials and parts by weight were the same. In order to determine the physical properties of the polyurethane prepared for each polyol, polyurethane was applied on a glass plate, Cracks) were confirmed.

As a result of the experiment, the degree of cracking was found to be as follows: ether polyol, Esterdiol (4) <pcd (COPOLYMER), Esterdiol (5) <pcd (homo), Esterdiol (1), Esterdiol ).

<Experimental Example 2_ Comparison of Physical Properties of Polyurethane Prepared by Diisocyanate Type>

In Experimental Example 2, polyisocyanates were prepared by diisocyanate in order to select the hard portion of the polyurethane.

division
Furtherance
Solids
(%)
Viscosity
(cps / 25 &lt; 0 &gt; C) after drying
Surface condition
(110 DEG C, 60 min) EPUD-1002-1 Esterdiol (1) / TDI / DMBA 45 1,800 clear EPUD-1002-2 Esterdiol (3) / MDI / CMDI / DMBA 45 3,500 crack EPUD-1002-3 Esterdiol (4) / MDI / DMBA 45 5,200 clear EPUD-1002-4 PCD (HOMO) / LMDI / DMBA 45 2,500 crack EPUD-1002-5 PTMG / Esterdiol (2)
/ TDI / LMDI / DMBA 45 3,900 crack EPUD-1002-6 PTMG / PCD (COPOLYMER)
/ TDI / MDI / DMBA 45 4,200 clear EPUD-1002-7 PTMG / PCD (Copolymer) / Esterdiol (3) / TDI / MDI / DMBA 45 3,800 clear EPUD-1002-8 PCD (COPOLYMER) / Esterdiol (4)
/ TDI / LMDI / DMBA 45 4,600 clear

The specific composition was as shown in Table 2, and the other raw materials and the weight parts were the same. In order to understand the physical properties of polyurethane synthesized by diisocyanate and diol, a polyurethane prepared on a glass plate was applied, dried, (Cracks) were confirmed.

Referring to FIG. 3, cracks were not generated on the surface when TDI was added to polyurethane, and cracks (cracks) occurred in the order of LMDI, MDI and CMDI.

On the other hand, as described above, the polyurethane that did not crack (crack) was applied to a glass plate and dried, and tensile strength (TS), elongation (EL), 100% modulus , The softening point (the temperature at which the refractory material softens by heat), and the tacky.

division TS
(kgf / cm ² )
EL
(%) 100%
modulus
(kgf / cm ² )
MP (占 폚)
Tacky EPUD-1001-1 - - - - √ EPUD-1001-2 - - - - √ EPUD-1001-6 - - - - √ EPUD-1001-9 130 450 50 120 - EPUD-1001-12 - - - - √ EPUD-1001-15 - - - - √ EPUD-1001-17 - - - - √ EPUD-1002-1 140 430 40 130 - EPUD-1002-3 - - - - √ EPUD-1002-6 200 380 75 145 - EPUD-1002-7 220 340 90 150 - EPUD-1002-8 250 280 80 150 -

EPUD-1001-1, EPUD-1001-2, EPUD-1001-6, EPUD-1001-12, EPUD-1001-15, EPUD-1001-17 and EPUD-1002, which have their own tacky -3 is not only difficult to confirm the physical properties of the final polyurethane but also is not suitable as a coating resin for producing a speaker damper.

Referring to Table 3 above, the polyurethane of EPUD-1002-7, which had a tensile strength of 220 kgf / cm ² , elongation of 340%, 100% modulus of 90 kgf / cm ² and a softening point of 150 ° C, It is most suitable as a coating resin for manufacturing a damper for use.

EXPERIMENTAL EXAMPLE 3 ______________________________________ Identification of Properties of Hybrid Resins Prepared by Type and Content of Epoxy Resin>

In Experimental Example 3, the physical properties of the hybrid resins differentiated according to the type of epoxy resin and the content of epoxy resin were compared.

After confirming the physical properties of the polyurethane in Experimental Examples 1 to 2, a relatively good polyurethane was selected and an epoxy resin was added.

Here, bisphenol A based epoxy resin, which is a typical epoxy resin, and Novolac Type Epoxy resin, which has excellent chemical resistance and adhesion, were used as the epoxy resin.

The specific types and contents of the epoxy resin were as shown in Table 4, and the other raw materials and the weight parts were the same. The hybrid resin prepared on the glass plate was coated on the glass plate for drying and drying The presence of surface cracks (cracks) was confirmed.

At this time, in case of EWB-1003-2, since the epoxy resin is not completely cured even after drying and there is stickiness in the state where the surface is migrated, it is difficult to confirm the physical properties of the hybrid resin, It was excluded because it was not suitable as resin.

division
Furtherance Epoxy content (parts by weight) tacky
Polyurethane Epoxy
Suzy 10 20 30 EWB-
1003-1 EPUD
-1001-9 BPA crack crack crack - NOVOLAC crack crack crack - EWB-
1003-2 EPUD
-1002-1 BPA clear clear clear √ NOVOLAC clear clear clear √ EWB-
1003-3 EPUD
-1002-6 BPA crack crack crack - NOVOLAC crack crack crack - EWB-
1003-4 EPUD
-1002-7 BPA clear clear crack - NOVOLAC clear clear crack - EWB-
1003-5 EPUD
-1002-8 BPA clear clear clear - NOVOLAC clear clear clear -

Referring to FIGS. 4A and 4B and Table 4, EWB-1003-1 and EWB-1003-3 were cracked regardless of the type and content of the epoxy resin.

Here, concrete physical properties of EWB-1003-4 and EWB-1003-5, which have the highest crack incidence rates, are compared as shown in Table 5 below.

division
Furtherance Properties
Polyurethane
Epoxy resin
(Parts by weight)
VIS
(cps / 25 &lt; 0 &gt; C)
TS
(kgf / cm ² )
EL
(%) 100%
mod
(kgf / cm ² )

EWB-
1003-4


EPUD
-1002-7
BPA 10 4,000 300 250 180 20 4,300 420 230 210
NOVOLAC 10 4,900 290 250 180 20 5,500 410 230 200

EWB-
1003-5



EPUD
-1002-8


BPA
10 5,000 280 220 160 20 5,400 390 180 190 30 6,000 510 130 210
NOVOLAC
10 5,300 290 230 160 20 5,900 380 190 185 30 6,700 500 155 205

Referring to Table 5, no significant difference according to the kind of epoxy resin occurred, but cracks (cracks) occurred when EWB-1003-4 exceeded 20 parts by weight of epoxy resin with respect to 100 parts by weight of polyurethane, In case of EWB-1003-5, crack (crack) did not occur but tensile strength was higher than EWB-1003-4, but it was found that the elongation was low.

Further, the viscosity after mixing of polyurethane and epoxy resin is lower than that of novolak type epoxy resin and lower than that of bisphenol A type epoxy resin, so that it is picked up on fabric by impregnation (degree of penetration of resin solution into fabric) .

Therefore, it is preferable to use a bis-phenol A based epoxy resin as the epoxy resin and 20 parts by weight of the epoxy resin per 100 parts by weight of the polyurethane.

<Experimental Example 4_ Selection of kinds and content of epoxy reaction accelerator>

In Experimental Example 4, the hardening rate and the hardness of the coating film were determined in order to select the type and content of the epoxy reaction promoter for promoting the epoxy reaction.

20 parts by weight of bisphenol A type epoxy resin having excellent properties confirmed in Experimental Example 3 was added to 100 parts by weight of polyurethane. The type and content of the epoxy reaction promoter were set as shown in Table 6, And the hardness (shore A) of the coating film was measured by drying. At this time, drying at 70 DEG C for 1 hour is an arbitrarily set condition.

Epoxy Reaction Promoter Drying time 0.2 phr 0.5 phr 1.0 phr TEDA 60 80 82 MI 65 85 86

Referring to Table 6, when the same amount of methylimidazole (MI) and triethylenediamine (TEDA) were added and the reaction rate of the epoxy resin was confirmed, methylimidazole was faster, and 0.5 phr It was confirmed that the effect on the addition amount was insufficient.

Therefore, methylimidazole is preferably used as the epoxy reaction promoter, and the content is preferably 0.4 to 0.6 phr based on the epoxy resin.

<Experimental Example 5_Curing Temperature and Time of Hybrid Resin>

In Experimental Example 5, a total of two tests were conducted to confirm the curing temperature and time at which water as a solvent is sufficiently volatilized. At this time, the curing temperature and time were confirmed on the basis of the point at which a coating film was formed on the hybrid resin and tacky was not generated.

At this time,? Indicates a state in which drying is insufficient,? Indicates a somewhat better state, and? Indicates an excellent state.

division 1 time Episode 2 sec ^{° C} 110 130 150 sec ^{° C} 110 130 150
EWB-
1003-4
60 ○ ◎ ◎ 60 △ ○ ○ 180 ◎ ◎ ◎ 180 ○ ○ ◎ 300 ◎ ◎ ◎ 300 ○ ◎ ◎

Referring to Table 7, it is preferable to cure at 130 to 150 ° C for 3 minutes to 5 minutes.

Experimental Example 6 Identification of Properties of Hybrid Resin [

In Experimental Example 6, the physical properties of the hybrid resin were determined according to the content of the curing agent, and water resistance, heat resistance and flexural property were measured using an amine-based curing agent.

First, to check the water resistance, a hybrid resin was coated on a release paper, a film was formed, and then impregnated in a 10% NaOH aqueous solution for 90 minutes and dried again to measure the weight of the sample.

In this case, X is the case where the film property retention is less than 70%,? Is from 70 to 80%,? Is from 80 to 90%, and? Is from 90 to 100%.

division Curing agent content (phr) 30 65 80 EWB-1003-4 ○ ◎ ◎

Referring to Table 8, when 30 phr of the curing agent was added, the retention of the physical properties was 80 to 90%. When 65 phr was added, the retention of the physical properties was 90 to 100%.

Even when 80 phr is added, the retention of the physical properties of 90 to 100% is shown. However, this is similar to the effect of adding 65 phr, but the production cost is increased and the physical properties are lowered.

Next, the softening point was measured to confirm the heat resistance of the hybrid resin. At this time, the softening point of the resin applicable to the speaker damper is preferably 250 ° C or higher.

division Curing agent content (phr) 30 65 80 EWB-1003-4 ○ ◎ ◎

Referring to Table 9, the softening point when 30 phr of the curing agent was added was measured at 220 to 250 ° C, and the softening point when 65 phr and 80 phr were added was measured at 250 ° C or more.

The softening point when 65 phr was added was measured at 250 ° C or higher. The softening point of 80 phr was also measured to be 250 ° C or higher, which is similar to that when 65 phr is added, but it is not suitable because the production cost is increased and the physical properties are lowered.

Next, the fabric was impregnated with a hybrid resin to confirm the bending resistance (resistance to bending from the external environment), and then the bending degree was measured using a flexo meter at -10 ° C.

division Curing agent content (phr) 30 65 80 EWB-1003-4 ◎ ◎ ○

X: Wrinkles are generated and collapsed when folded.

△: When folded, wrinkles occur largely but when wrinkled, wrinkles disappear immediately.

○: When folded, a little wrinkle occurs, but when folded, wrinkles disappear immediately.

◎: It is difficult to cause wrinkles when folded.

Referring to FIGS. 5 and 10, the lower the content of the curing agent, the better the result. However, since the curing agent was not sufficiently cured, the physical properties could be deteriorated, and the flexural resistance was decreased as the amount of the curing agent was increased and the crosslinking density was increased.

5 (A) shows the curvature of the hybrid resin to which 80 phr of the curing agent is added, and FIG. 5 (B) shows the curvature of the hybrid resin to which 30 phr of the curing agent is added. C) can confirm the flexural strength of the hybrid resin to which 65 phr of the curing agent is added.

As a result of comparing the physical properties of the hybrid resin by measuring the water resistance, heat resistance and bending property, the physical properties of the hybrid resin added with 65 phr of amine type curing agent to the epoxy resin were most suitable for the coating resin of the speaker damper.

The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the claims of the invention to be described below may be better understood. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the appended claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (10)

Ether-based polyol and carbonate-based polyol together with an aromatic diisocyanate and a glycol having a weight average molecular weight of 60 to 200 to synthesize a polyurethane and emulsify it with water;
A second step of mixing and stirring the polyurethane and the epoxy resin with each other to prepare a hybrid resin; And
A third step of adding an amine-based, amide-based or acid anhydride-based curing agent and an epoxy reaction promoter to the hybrid resin and curing the mixture;
Wherein the water-based polyurethane / epoxy hybrid resin for a speaker damper comprises a water-based polyurethane / epoxy hybrid resin. The method according to claim 1,
In the first step,
Wherein the polyisocyanate is 20 to 40 parts by weight of the polyol, 5 to 15 parts by weight of the aromatic diisocyanate, and 3 to 10 parts by weight of the glycol having a weight-average molecular weight of 60 to 200, relative to 50 to 60 parts by weight of the water. A method for producing a polyurethane / epoxy hybrid resin. The method according to claim 1,
In the first step,
Wherein the polyol is a mixture of polycarbonate diol (PCD) and polytetramethylene glycol (PTMG). The method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper according to claim 1, The method according to claim 1,
In the first step,
Wherein the aromatic diisocyanate is a mixture of toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI), and the aromatic diisocyanate is mixed with toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI) to prepare an aqueous polyurethane / epoxy hybrid resin for speaker damper. The method according to claim 1,
In the first step,
An additive including an antioxidant, a UV stabilizer and an emulsifier is further added,
Wherein the content of the additive is 0.2 to 2.0 parts by weight based on 50 to 60 parts by weight of the water. The method according to claim 1,
In the first step,
Wherein the polyurethane is produced at 50 to 90 占 폚 for 10 to 15 hours. The method for producing an aqueous polyurethane / epoxy hybrid resin for a speaker damper according to claim 1, The method according to claim 1,
In the second step,
Wherein the epoxy resin is 20 parts by weight based on 100 parts by weight of the polyurethane. The method according to claim 1,
In the second step,
The content of the crosslinking agent is 60 to 70 phr with respect to the epoxy resin,
Wherein the hybrid resin is produced at 10 to 35 DEG C for 1 to 3 hours. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
In the third step,
The content of the curing agent is 60 to 70 phr with respect to the epoxy resin,
Wherein the content of the epoxy reaction promoter is 0.5 to 2.0 phr with respect to the epoxy resin. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
In the third step,
Wherein the hybrid resin is cured at 130 to 150 DEG C for 3 to 5 minutes. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;

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