WO2020036443A1 - Low-friction resin composite - Google Patents

Abstract

The present invention relates to a low-friction resin composite. The low-friction resin composite has excellent heat resistance and a low-friction coefficient, thereby enabling a material for a relative friction component having excellent durability and low-friction properties to be provided.

Description

Low Friction Resin Composite

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0096135 dated August 17, 2018 and Korean Patent Application No. 10-2019-0099149 dated August 13, 2019. All content disclosed in the literature is included as part of this specification.

The present invention relates to a resin composite having low friction properties and excellent heat resistance and a material for relative friction parts using the same.

Recently, in the automobile industry, in order to increase energy efficiency, much effort has been made to reduce friction at energy transmission units such as power trains and drive trains. This is because only 15% of the fuel used in automobiles is delivered to the wheels, of which 10% are lost due to drive friction.

Accordingly, plastic materials are used in addition to metal products in order to reduce drive friction. Friction parts made from these plastic materials are self-lubricating, which greatly helps to reduce the losses due to friction. However, in an environment where high rotation and pressure are generated, a problem arises in that the friction parts made of the plastic material are deformed or fused due to the heat generated by the friction.

As a result, high heat-resistant super-engineering such as PEEK (polyether ether ketone), PAI (polyamide imide), PI (polyimide), etc., which have high heat resistance and low friction characteristics as relative friction parts such as bearings, bushings, thrust washers, or oil seals. Plastic is mainly used. However, PEEK is still inadequate for parts exposed to very high pressure and high speed environments due to its relatively low heat resistance, and PAI and PI have limited application to parts due to low processability and productivity and high price.

The present invention is to provide a low friction resin composite having high heat resistance and excellent processability and exhibiting improved low friction properties.

In addition, the present invention is to provide a material for counter friction parts manufactured using the low friction resin composite.

According to the present invention, there is provided a binder comprising a phthalonitrile-based resin and a low friction resin composite including three or more fillers on the binder.

In addition, according to the present invention, there is provided a material for counter friction parts manufactured using the low friction resin composite.

Hereinafter, a low friction resin composite according to embodiments of the present invention and a material for counter friction parts manufactured using the same will be described in detail.

Prior to this, the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention unless expressly stated otherwise.

As used herein, the singular forms “a,” “an,” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

As used herein, the meaning of "includes" specifies a particular property, region, integer, step, operation, element, and / or component, and other specific properties, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.

I. Low Friction Resin Composites

According to one embodiment of the invention,

A low friction resin composite comprising a binder comprising a phthalonitrile-based resin and at least three fillers dispersed on the binder is provided.

As a result of continuous research by the present inventors, it was confirmed that a resin composite including a binder containing a phthalonitrile-based resin and three or more fillers dispersed on the binder may exhibit improved low friction properties while having excellent heat resistance and processability. It became.

The low friction resin composite makes it possible to provide a material for relative friction parts having excellent durability and low friction characteristics even in an ultrahigh pressure and high speed environment.

(1) binder

The low friction resin composite includes a phthalonitrile resin as a binder.

Specifically, the binder including the phthalonitrile-based resin, the composition containing the phthalonitrile compound may be one that is cured by at least one curing agent selected from the group consisting of amine compound, hydroxy compound and imide compound have.

The phthalonitrile compound has two or more, or 2 to 20, or 2 to 16, or 2 to 12 phthalonitrile structures capable of forming a phthalonitrile resin through reaction with the curing agent. It may be a compound containing 2 to 8, or 2 to 4.

Preferably, the phthalonitrile compound may be at least one compound selected from the group consisting of a compound represented by the average composition formula of Formula 1 and a compound represented by the average composition formula of Formula 5.

[Formula 1]

In Chemical Formula 1,

R ¹¹ are each independently a substituent of Formula 2,

Each R ¹² is independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group,

a, b and c are positive numbers,

d, e and f are zero or a positive number,

a + b + c + d + e + f is 1;

[Formula 2]

In Chemical Formula 2,

X is a group connected to the silicon atom in the formula (1), a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, alkylene group, alkenylene group, alkynylene group, -C (= O) -X ¹ -or -X ¹ -C (= O)-, wherein X ¹ is an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group,

R ²¹ to R ²⁵ are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a cyano group, or a substituent of Formula 3 below, wherein at least one of R ²¹ to R ²⁵ is a substituent of Formula 3 below;

[Formula 3]

In Chemical Formula 3,

Y is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, alkylene group, alkenylene group, alkynylene group, -C (= O) -X ¹ -or -X ¹ -C (= O)-, X ¹ is an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group,

R ³¹ to R ³⁵ are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, or a cyano group, and at least two of R ³¹ to R ³⁵ are cyano groups.

In the present specification, that the phthalonitrile compound is represented by a specific average composition formula means that the phthalonitrile compound is a single compound represented by the composition formula.

In this specification, the phthalonitrile compound represented by a specific average composition formula means that the phthalonitrile compound is a mixture of two or more different compounds and is represented by the composition formula when the average of the composition represented by the mixture is taken. do.

The compound represented by the average compositional formula of Formula 1 is a polymer or oligomeric compound, for example, the weight average molecular weight (Mw) is 1000 to 50000 g / mol, or 2500 to 35000 g / mol, or 4000 to 20000 g / mol, or in the range of 6000 to 9000 g / mol.

Compound represented by the average composition formula of Formula 1 has a weight average molecular weight in the above range, it is possible to provide a polymerizable composition having a low processing temperature and / or a wide process window.

As used herein, the term weight average molecular weight is a conversion value with respect to standard polystyrene measured using a gel permeation chromatograph (GPC), and the term molecular weight herein means weight average molecular weight unless otherwise specified.

For example, molecular weight is measured using an Agilent PL-GPC 220 instrument equipped with a PLgel MIXED-B column (Polymer Laboratories) of 300 mm length. The measurement temperature was 160 ° C., 1,2,4-trichlorobenzene was used as the solvent and the flow rate was measured at a rate of 1 mL / min. Samples are prepared at a concentration of 10 mg / 10 mL and then supplied in an amount of 200 μL. The values of Mw and Mn are derived based on the calibration curve formed using the polystyrene standard. The molecular weight (g / mol) of the polystyrene standard uses 9 kinds of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

Preferably, the compound represented by the average composition formula of Formula 1 may be a compound represented by the following formula (4):

[Formula 4]

In Chemical Formula 4,

R ¹¹ and R ¹² are each as defined in Chemical Formula 1,

n and m are each a number selected in the range of 1 to 100 and satisfy 2 ≦ n + m ≦ 100.

Preferably, in Formula 4, n + m is 2 to 100, or 2 to 80, or 2 to 50. The compound satisfying the range of n + m makes it possible to provide a polymerizable composition having excellent processability.

[Formula 5]

In Chemical Formula 5,

R ⁵¹ is a substituent of Formula 6,

Each R ⁵² is independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group,

a is a number in the range of 0.01 to 0.4,

b is a number in the range of 0.5 to 4;

[Formula 6]

In Chemical Formula 6,

X 'is a group connected to the silicon atom in the formula (5), a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, alkylene group, alkenylene group, alkynylene group, -C ( = O) -X ¹ -or -X ¹ -C (= O)-, wherein X ¹ is an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group ,

R ⁶¹ to R ⁶⁵ are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a cyano group, or a substituent of Formula 7, wherein at least one of R ⁶¹ to R ⁶⁵ is a substituent of Formula 7;

[Formula 7]

In Chemical Formula 7,

Y 'is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, alkylene group, alkenylene group, alkynylene group, -C (= O) -X ¹ -or -X ^1- C (= 0)-, X ¹ is an oxygen atom, a sulfur atom, -S (= 0) _2- , an alkylene group, an alkenylene group or an alkynylene group,

R ⁷¹ to R ⁷⁵ are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, or a cyano group, and ^at least two of R ⁷¹ to R ⁷⁵ are cyano groups.

The compound represented by the average compositional formula of Formula 7 is a compound in the form of a polymer or oligomer, for example, the weight average molecular weight (Mw) of 700 to 7000 g / mol, or 700 to 6500 g / mol, or 700 to 5800 g / mol, or in the range of 700 to 5000 g / mol.

Compound represented by the average formula of Formula 7 has a weight average molecular weight in the above range, it is possible to provide a polymerizable composition having a low processing temperature and / or a wide process window.

Preferably, the compound represented by the average composition formula of Formula 7 may be a compound represented by the following formula (8):

[Formula 8]

In Chemical Formula 8,

R ⁵¹ and R ⁵² are the same as defined in Chemical Formula 5,

n is a number in the range of 3 to 100.

N in Formula 8 is 5 or more, or 7 or more; And 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, or 60 or less.

Preferably, the phthalonitrile compound may be a compound represented by the following formula (P1).

[Formula P1]

In formula P1, R R ^P11 to ^P16 each independently represent a hydrogen, an alkoxy group of the alkyl group, C _1-5 of C _1-5, an aryl group, a group the formula P2, P3 or the formula a group of C _6-30 , At least two of R ^P11 to R ^P16 may be represented by the following Chemical Formula P2 group or Chemical Formula P3 group,

[Formula P2]

In Chemical Formula P2,

L ^P2 is a direct bond, an alkylene group of C _1-5 , -O-, -S-, -C (= 0)-, -S (= 0)-, or -S (= 0) _2- ,

R R ^P21 to ^P25 are two or more of each independently represent a hydrogen, an alkoxy group, an aryl group, a cyano group, a C _6-30 alkyl group a, C _1-5 of C _1-5, the R R ^P21 to ^P25 is a cyano group to be,

[Formula P3]

In Chemical Formula P3,

L ^P3 is a direct bond, an alkylene group of C _1-5 , -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) _2- , -C ( CH ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= 0) NH-,

R R ^P31 to ^P35 are each independently a hydrogen, an alkyl group, an alkoxy group, an aryl group, the P2 group of the formula C _6-30 of C _1-5, and one or more of the R R ^P31 to ^P35 of the C _1-5 is The above formula is P2 group.

As used herein, an "alkyl group" may be straight or branched chain. Preferably, the alkyl group has 1 to 5 carbon atoms or 1 to 3 carbon atoms. Specifically, the alkyl group is methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n- Pentyl, isopentyl, neopentyl, tert-pentyl and the like.

As used herein, an "aryl group" may be a monocyclic aryl group or a polycyclic aryl group. Preferably, the aryl group has 6 to 30 carbon atoms. Specifically, the aryl group may be a phenyl group, a biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group and the like.

As used herein, "direct bond" means that no atoms are present in the group and groups on both sides are directly connected to each other.

According to an embodiment of the invention, the phthalonitrile compound may be a compound represented by the following formula P1 '.

[Formula P1 ']

In the formula P1 ',

L ^P2 and L ^P3 are each independently a direct bond, an alkylene group of C _1-5 , -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= 0) NH-.

As a non-limiting example, a compound in which L ^P2 is -O- and L ^P3 is a direct bond or a methylene group may be used as the phthalonitrile compound.

In addition to the phthalonitrile compounds described above, examples of the phthalonitrile compounds include U.S. Patent 4,408,035, U.S. Patent 5,003,039, U.S. Patent 5,003,078, U.S. Patent 5,004,801, U.S. Patent 5,132,396, U.S. Patent 5,139,054 Compounds known in US Pat. No. 5,208,318, US Pat. No. 5,237,045, US Pat. No. 5,292,854, or US Pat. No. 5,350,828, and the like. Compounds can be included in the examples above.

On the other hand, the curing agent of the phthalonitrile compound is not particularly limited as long as it can react with the phthalonitrile compound to form a phthalonitrile resin.

For example, one or more compounds selected from the group consisting of amine compounds, hydroxy compounds and imide compounds may be used as the curing agent. The amine compound, the hydroxy compound and the imide compound mean a compound including at least one amino group, hydroxy group and imide group in the molecule, respectively.

Preferably, the curing agent may be an imide compound represented by Formula 9 below:

[Formula 9]

In Chemical Formula 9,

M is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound,

X ¹ and X ² are each independently a divalent radical derived from an alkylene group, an alkylidene group, or an aromatic compound,

n is a number of 1 or more.

The imide-based compound represented by Formula 9 exhibits excellent heat resistance by including an imide structure in a molecule, so that it is excessively contained in the polymerizable composition or adversely affects physical properties even when the polymerizable composition is processed or cured at a high temperature. Do not cause defects such as voids that may be caused.

In Formula 9, M may be a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound. In the aliphatic, alicyclic or aromatic compound, radicals formed by leaving four hydrogen atoms in a molecule may each have a structure in which a carbon atom of the carbonyl group of Formula 9 is connected.

Specifically, as the aliphatic compound, alkane, alkenes, or alkynes which are linear or branched may be exemplified. As the aliphatic compound, alkanes, alkenes, or alkynes having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms may be used. The alkanes, alkenes, or alkynes may be optionally substituted by one or more substituents.

Examples of the alicyclic compound include hydrocarbon compounds having a non-aromatic ring structure having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 3 to 4 carbon atoms. Such an alicyclic hydrocarbon compound may include at least one hetero atom, such as oxygen or nitrogen, as a ring constituent atom, and may be optionally substituted with one or more substituents if necessary.

As said aromatic compound, benzene, the compound containing benzene, or derivatives thereof can be illustrated. As the compound including the benzene, a compound having a structure in which two or more benzene rings are condensed while sharing one or two carbon atoms, or connected by a directly linked structure or an appropriate linker.

Examples of linkers applied to linking the two benzene rings include an alkylene group, an alkylidene group, -O-, -S-, -C (= 0)-, -S (= 0)-, and -S (= O) _2- , -C (= O) -OL ¹ -OC (= O)-, -L ² -C (= O) -OL ^3- , -L ⁴ -OC (= O) -L ^5- , Or -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ⁸ -and the like.

L ¹ to L ⁸ may be each independently a single bond, —O—, an alkylene group, or an alkylidene group, and Ar ¹ and Ar ² may each independently be an arylene group.

The aromatic compound may include, for example, 6 to 30, 6 to 28, 6 to 27, 6 to 25, 6 to 20 or 6 to 12 carbon atoms. It may be substituted by one or more substituents if necessary. The number of carbon atoms of the aromatic compound is a number including the carbon atoms present in the linker when the compound contains the linker described above.

Specifically, in Formula 9, M may be a tetravalent radical derived from an alkane, alkene, or alkyne, or a tetravalent radical derived from a compound represented by one of the following Formulas 10 to 15:

[Formula 10]

In Formula 10, R ¹⁰¹ to R ¹⁰⁶ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group;

[Formula 11]

In Formula 11, R ¹¹¹ to R ¹¹⁸ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group;

[Formula 12]

In Chemical Formula 12,

R ¹²⁰ to R ¹²⁹ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group,

X is a single bond, an alkylene group, an alkylidene group, -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) _2- , -C (= O ) -OL ¹ -OC (= O)-, -L ² -C (= O) -OL ^3- , -L ⁴ -OC (= O) -L ^5- , or -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ^8- , wherein L ¹ to L ⁸ are each independently a single bond, -O-, an alkylene group, or an alkylidene group, and Ar ¹ and Ar ² are each independently an arylene group.

At this time, in the present specification, a single bond means a case where an atom does not exist in the portion. Therefore, when X in Formula 12 is a single bond, it means a case where no atom is present in the moiety represented by X. In this case, the benzene rings on both sides of X may be directly connected to form a biphenyl structure.

In Chemical Formula 12, -C (= 0) -OL ¹ -OC (= 0)-, -L ² -C (= 0) -OL ^3- , or -L ⁴ -OC (= 0)-in X. L ⁵ - in L ¹ to L ⁵ are each independently, having 1 to 12 carbon atoms, having 1 to 8 carbon atoms, or carbon atoms can be an 1 alkylene group or alkylidene of 1 to 4, wherein the alkylene group or alkylidene group is a substituted or unsubstituted It may be.

In addition, in X of Chemical Formula 12, -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ^8- , wherein L ⁶ and L ⁸ may be -O-, L ⁷ has 1 to 12 carbon atoms, and 1 to 1 carbon atoms. Or an alkylene group or an alkylidene group having 1 to 4 carbon atoms, and the alkylene group or alkylidene group may be substituted or unsubstituted. Ar ¹ and Ar ² may be a phenylene group, in which case L ⁶ and L ⁸ based on L ⁷ may be connected to the ortho, meta or para position of the phenylene, respectively.

[Formula 13]

In Chemical Formula 13,

R ¹³¹ to R ¹³⁴ are each independently hydrogen, an alkyl group, or an alkoxy group, two of R ¹³¹ to R ¹³⁴ may be connected to each other to form an alkylene group,

A is an alkylene group or alkenylene group, wherein the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom;

[Formula 14]

In Formula 14, R ¹⁴¹ to R ¹⁴⁴ are each independently hydrogen, an alkyl group, or an alkoxy group, and A is an alkylene group;

[Formula 15]

In Formula 15, R ¹⁵⁰ to R ¹⁵⁹ are each independently hydrogen, an alkyl group, or an alkoxy group.

The tetravalent radical derived from the compound represented by the above formulas (10) to (15) is formed by directly leaving the substituents of the above formulas (10) to (15), or in the examples of the substituents, an alkyl group, an alkoxy group, an aryl group, an alkylene group or an alkenylene group The belonging hydrogen atom may be separated and formed.

For example, when the tetravalent radical is derived from a compound of Formula 10, at least one, at least two, at least three or four of R ¹⁰¹ to R ¹⁰⁶ of Formula 10 form a radical or R ¹⁰¹ To a hydrogen atom of the alkyl group, alkoxy group, or aryl group present in R ¹⁰⁶ may be released to form a radical. Forming a radical in the above may mean that the site is connected to the carbon atom of the carbonyl group of formula 9 as described above.

In addition, when the tetravalent radical is derived from a compound of Formula 12, R ¹²⁰ to R ¹²⁹ of Formula 12 each independently represent a hydrogen, an alkyl group, an alkoxy group or an aryl group, and at least one, at least two, and at least three Or more or four may form a radical linked to formula (9). Each of which does not form a radical in the above may be hydrogen, an alkyl group or an alkoxy group, or may be hydrogen or an alkyl group. In one example, in Formula 12, any two of R ¹²⁷ to R ¹²⁹ and any two of R ¹²² to R ¹²⁴ may form the radical, and the other substituents are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, It may be a hydrogen, an alkyl group or an alkoxy group, or may be a hydrogen or an alkyl group.

As a non-limiting example, the compound represented by Formula 10 may be benzene or 1,2,4,5-tetraalkylbenzene.

As a non-limiting example, the compound represented by Formula 12 may be biphenyl or a compound represented by one of the following Formulas A to F:

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

Formula F]

The compound represented by Formula 13 may be a cycloalkane having 4 to 8 carbon atoms such as cyclohexane, a cycloalkene having 4 to 8 carbon atoms such as cyclohexene which may be substituted with one or more alkyl groups, or any one of the following Formulas G to I It may be a compound represented by the formula:

[Formula G]

[Formula H]

[Formula I]

The compound represented by Chemical Formula 14 may be represented by Chemical Formula J or a compound in which at least one hydrogen of the compound represented by Chemical Formula J is substituted with an alkyl group:

[Formula J]

In Formula 9, X ¹ and X ² may each independently be a divalent radical derived from an aromatic compound. For example, X ¹ and X ² may each independently be a divalent radical derived from an aromatic compound having 6 to 40 carbon atoms. The divalent radical derived from the said aromatic compound is replaced by the content mentioned above.

Specifically, in Formula 9, X ¹ and X ² may each independently be a divalent radical derived from a compound represented by any one of Formulas 16 to 18:

[Formula 16]

In Formula 16, R ¹⁶¹ to R ¹⁶⁶ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group;

[Formula 17]

In Chemical Formula 17,

R ¹⁷⁰ to R ¹⁷⁹ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group,

X 'is -C (= O) a single bond, an alkylene group, an alkylidene group, -O-, -S-, -, -S (= O) - - -NR a,, -S (= O) 2 - , -L ⁹ -Ar ³ -L ¹⁰ -or -L ¹¹ -Ar ⁴ -L ¹² -Ar ⁵ -L ^13- , wherein R ^a is hydrogen, an alkyl group, an alkoxy group, or an aryl group, and L ⁹ to L ¹³ are each independently a single bond, —O—, an alkylene group, or an alkylidene group, and Ar ³ to Ar ⁵ are each independently an arylene group;

[Formula 18]

In Formula 18, R ¹⁸⁰ to R ¹⁸⁹ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group.

The divalent radical derived from the compound represented by the above formulas (16) to (18) is formed by directly leaving the substituents of the above formulas (16) to (18), or in the examples of the substituents, an alkyl group, an alkoxy group, an aryl group, an alkylene group or an alkenylene group. The hydrogen atom to which it belongs may leave and formed.

For example, when the divalent radical is derived from the compound represented by Formula 16, and is, for example, phenylene, the substitution position of the amine group based on the site linked to N in X ¹ of Formula 9 is represented by ortho ( ortho, meta or para position, and the substitution position of the amine group based on the site linked to N in X ² of Formula 9 is also ortho, meta or para. (para) location.

In addition, when the divalent radical is derived from a compound represented by Formula 17, R ¹⁷⁷ of Formula 17 To any of R ¹⁷⁹ and any of R ¹⁷² to R ¹⁷⁴ of Formula 17 may form a radical connected to a nitrogen atom of Formula 9. Other substituents other than the substituents forming the radicals may each independently be hydrogen, an alkyl group, an alkoxy group or an aryl group, a hydrogen, an alkyl group or an alkoxy group, or may be a hydrogen or an alkyl group.

As a non-limiting example, the compound represented by Formula 16 is benzene which may be substituted with at least one hydroxy group or carboxyl group.

The compound represented by Formula 17 may be a biphenyl which may be substituted with at least one hydroxy group or a carboxyl group, a compound that may be substituted with at least one hydroxy group or a carboxyl group while being represented by any one of Formulas A to F, or the following Formula It is a compound which may be substituted with at least one hydroxy group or carboxyl group represented by K or M.

[Formula K]

[Formula L]

[Formula M]

The compound represented by Chemical Formula 18 is a compound represented by the following Chemical Formula N, or at least one of hydrogen of the compound represented by the following Chemical Formula N is substituted with a hydroxyl group or a carboxyl group:

[Formula N]

In the present specification, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched, or cyclic and may be substituted by one or more substituents if necessary.

In the present specification, the alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched, or cyclic and may be substituted by one or more substituents if necessary.

In the present specification, an aryl group may mean a monovalent moiety derived from the aforementioned aromatic compound, unless otherwise specified.

In the present specification, an alkylene group or an alkylidene group is an alkylene group or an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. Can mean. The alkylene group or alkylidene group may be linear, branched, or cyclic. In addition, the alkylene group or alkylidene group may be optionally substituted with one or more substituents.

In the present specification, as the substituent which may be optionally substituted with an aliphatic compound, an alicyclic compound, an aromatic compound, an alkyl group, an alkoxy group, an aryl group, an alkylene group, or an alkylidene group, halogen, glycine such as chlorine or fluorine Epoxy groups, such as a dill group, an epoxy alkyl group, a glycidoxy alkyl group, or an alicyclic epoxy group, an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, an aryl group, etc. can be illustrated.

In Formula 9, n means the number of imide repeat units, 2 to 200, 2 to 150, 2 to 100, 2 to 90, 2 to 80, 2 to 70, 2 to 60, 2 to 50, 2 It may be a number in the range from 40 to 2, 30 to 20, or 2 to 10.

When n is 2 or more in Formula 9, that is, when the compound of Formula 9 is a polyimide compound, it may be more advantageous in terms of heat resistance and strength. Therefore, in the case of the material for counter friction parts including phthalonitrile resin cured using a polyimide compound, it has higher heat resistance and can prevent deformation and fusion of phthalonitrile resin under high pressure and high pressure conditions, and higher strength This can result in low wear and high durability.

As a non-limiting example, the curing agent may be a compound represented by Formula C1 or Formula C2.

[Formula C1]

[Formula C2]

In Chemical Formulas C1 and C2,

X and X 'are each independently a direct bond, a C _1-5 alkylene group, -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) ₂ -, -C (= O) -OL ¹ -OC (= O)-, -L ² -C (= O) -OL ^3- , -L ⁴ -OC (= O) -L ^5- , or -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ^8- ; Wherein L ¹ to L ⁸ are each independently a direct bond, -O-, or a C _1-5 alkylene group; Ar ¹ and Ar ² are each independently a C _6-30 arylene group,

R ⁹⁰ to R ⁹⁹ each independently is hydrogen, an alkoxy group, an aryl group, a hydroxy group of a C _6-30 alkyl group, C _1-5 of C _1-5, or a carboxyl group.

The compound represented by Chemical Formula 9 may be synthesized according to a known method for synthesizing an organic compound, and the specific manner thereof is not particularly limited. For example, the compound represented by the formula (9) can be formed by a dehydration condensation reaction of a dianhydride compound and a diamine compound.

Compound represented by the formula (9) has a high boiling point, does not volatilize or decompose at high temperatures, thereby maintaining a stable curability of the polymerizable composition, a void that may adversely affect physical properties during high temperature processing or curing process does not form a void. Accordingly, the compound may have a decomposition temperature of 300 ° C. or higher, 350 ° C. or higher, 400 ° C. or higher, or 500 ° C. or higher. The decomposition temperature may mean a temperature at which a decomposition rate of the compound represented by Formula 9 is maintained in a range of 10% or less, 5% or less, or 1% or less. The upper limit of the decomposition temperature is not particularly limited, but may be, for example, about 1000 ° C. or less.

The compound represented by the formula (9) is a process window of the reactive or polymerizable composition itself, i.e., melting of the polymerizable composition or a prepolymer formed therefrom by selection of X ¹ or X ² which is M or a linker of the core. Since the difference between temperature and hardening temperature can be adjusted easily, it can act as a hardening | curing agent of various physical properties according to a use.

(2) filler

The low friction resin composite includes a filler dispersed on the binder as an additive.

The filler is dispersed on the binder to reduce the erosion on the opposite surface in the ultra high pressure and ultra high speed environment to enable the expression of wear resistance.

Preferably, by applying three or more fillers to the low friction resin composite, it is possible to secure appropriate wear resistance and low friction coefficient.

For the expression of the above-mentioned properties, the filler may be graphite, polytetrafluoroethylene (PTFE), tungsten disulfide (WS ₂ ), molybdenum disulfide (MoS ₂ ), and pulverized At least three additives selected from the group consisting of milled carbon fibers (mCF) are preferably applied.

More preferably, the filler comprises graphite; Further comprising at least two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and pulverized carbon fibers is advantageous for the expression of the above-mentioned properties.

The graphite may be preferably applied by enabling the expression of excellent low friction properties and proper wear resistance while having a relatively low density and cost among the above-described fillers.

As a non-limiting example, the low friction resin composite includes a filler

Graphite, polytetrafluoroethylene, and tungsten disulfide; or

Graphite, polytetrafluoroethylene, and molybdenum disulfide; or

Graphite, polytetrafluoroethylene, and ground carbon fibers; or

Graphite, tungsten disulfide, and molybdenum disulfide; or

Graphite, tungsten disulfide, and ground carbon fiber; or

Graphite, molybdenum disulfide, and ground carbon fiber; or

Graphite, polytetrafluoroethylene, tungsten disulfide, and molybdenum disulfide; or

Graphite, polytetrafluoroethylene, tungsten disulfide, and ground carbon fibers; or

Graphite, polytetrafluoroethylene, molybdenum disulfide, and ground carbon fiber; or

Graphite, tungsten disulfide, molybdenum disulfide, and ground carbon fiber; or

Graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and ground carbon fibers can be included.

If necessary, the low friction resin composite may be formed of glass fiber, titanium oxide, antimony trisulfide, antimony trioxide, barium sulfate, calcium hydroxide, calcium carbonate, magnesium oxide, calcium fluoride, silica, alumina, iron oxide, or oxide in addition to the fillers exemplified above. It may further include one or more particles selected from the group consisting of chromium, zirconium oxide, boron nitride, carbon nanotubes, and graphene.

It is preferable that the said filler is a powdery additive which has the longest diameter of 0.01-100 micrometers which consists of the above-mentioned raw material. Here, when the fine particles constituting the powder is spherical, the longest diameter means the diameter of the fine particles. When the fine particles constituting the powder are not spherical, the longest diameter means the longest diameter at the center cut surface of the fine particles.

The particle size of the fine particles can be measured using a particle size analyzer (typically available through HORIBA, etc.) according to ASTM E 799-03 (Standard Practice for Determining Data Criteria and Processing for Liquid Drop Size Analysis).

When the size of the fine particles constituting the powder is too small, the filler may be easily aggregated during the preparation of the low friction resin composite, thereby making it difficult to express uniform physical properties. In addition, when the size of the fine particles is too small, the number of inner layers of the particles that can be lubricated may be reduced, and thus may not serve as lubricants.

Even when the size of the fine particles constituting the powder is too large, it is difficult to uniformly disperse the filler during the production of the low friction resin composite, it may be difficult to express the targeted low friction characteristics.

The filler may be included in an amount of 1 to 100 parts by weight based on 100 parts by weight of the binder including the phthalonitrile-based resin.

Specifically, with respect to 100 parts by weight of the binder, the filler is at least 1 part by weight, or at least 5 parts by weight, or at least 10 parts by weight, or at least 20 parts by weight, or at least 30 parts by weight, or at least 40 parts by weight; And 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less, or 60 parts by weight or less, or 50 parts by weight or less.

Preferably, with respect to 100 parts by weight of the binder, the filler is 1 to 100 parts by weight, or 5 to 100 parts by weight, or 5 to 90 parts by weight, or 10 to 90 parts by weight, or 10 to 80 parts by weight, or 15 to 80 parts by weight, or 20 to 80 parts by weight, or 20 to 70 parts by weight, or 30 to 70 parts by weight, or 30 to 60 parts by weight, or 40 to 60 parts by weight.

When the content of the filler is too small, the low friction resin composite may not have a sufficiently low coefficient of friction and adequate wear resistance. In addition, when the content of the filler is too high, it may not impart sufficient strength to the low friction resin composite, and thus may be destroyed under high speed and high pressure conditions or by impact.

For example, the low friction resin composite is based on 100 parts by weight of the binder including the phthalonitrile-based resin; 15 to 30 parts by weight of graphite; 10 to 40 parts by weight of two kinds of additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and pulverized carbon fibers.

As another example, the low friction resin composite is based on 100 parts by weight of the binder including the phthalonitrile-based resin; 20 to 25 parts by weight of graphite; 15 to 35 parts by weight of two kinds of additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and pulverized carbon fibers.

(3) Physical Properties of Low Friction Resin Composites

In order to determine whether the low friction resin composite exhibits low friction characteristics, friction coefficients were determined based on ASTM D3702 (Standard Test Method for Wear Rate and Coefficient of Friction of Materials in Self-Lubricated Rubbing Contact Using a Thrust Washer Testing Machine). You can measure it.

In particular, as can be seen in the examples described later, the low friction resin composite exhibits a low coefficient of friction under conditions of high pressure and high rotation speed with respect to the friction material, it can be confirmed that it can be applied as a material for relative friction parts of automobiles have.

The ASTM D3702 specification is intended to measure the coefficient of friction and wear rate of thrust washer specimens to ensure that they are suitable for use as self-lubricating materials.

In the present invention, the friction coefficient and wear rate were measured according to the ASTM D3702 standard using a friction coefficient measuring instrument as shown in FIG. 1.

Specifically, the method of obtaining the coefficient of friction and the wear rate by the ASTM D3702 standard is as follows:

1) The low friction resin composite is fabricated into a test specimen having the size and thickness specified in ASTM D3702.

2) Install the specimen in the upper specimen holder of the friction coefficient measuring instrument.

3) Install the friction material in the lower stationary specimen holder of the friction coefficient meter (in the case of FIG. 1, the steel washer is installed as the friction material).

4) Set a specific pressure (P) and rotation speed (V) on the friction coefficient measuring device, so that the friction coefficient under the desired PV Value (multiplied pressure and speed) condition (

) Can be obtained by the following formula (1).

[Equation 1]

In Formula 1,

T is the torque applied to the specimen (Nm), r is the radius of the specimen (mm), and W is the vertical force (kg).

In addition, the wear rate is measured by dividing the mass change before and after the experiment by the density, and then the wear volume obtained through this, and the reduced thickness per second based on the reduced thickness obtained by dividing the obtained volume change by the area of the ring (10 ^-10 m). / s)

The low friction resin composite measured friction coefficient for a thrust washer specimen having a contact area of 1.3 cm ² based on the friction carbon steel under the condition that the PV value was 2.3 MPa · m / s according to ASTM D3702 standard. Thermal deformation may not occur. That is, the low friction resin composite according to the embodiment can withstand the speed and pressure in a lubricating environment with a PV value of 2.3 MPa · m / s.

Specifically, the low friction resin composite is a thrust washer specimen having a contact area of 1.3 cm ² based on the friction material carbon steel under the condition that the PV value is 2.3 MPa · m / s based on the ASTM D3702 standard. The coefficient of friction in the non-lubricating (self-lubricating) conditions measured for may be 0.175 or less.

Specifically, the friction coefficient under the non-lubricating (self-lubricating) condition may be 0.175 or less, or 0.170 or less, or 0.165 or less. Preferably, the friction coefficient is 0.050 to 0.175, or 0.055 to 0.175, or 0.055 to 0.170, or 0.060 to 0.170, or 0.060 to 0.165, or 0.065 to 0.165, or 0.070 to 0.165, or 0.075 to 0.165, or 0.080 to 0.165, or 0.085 to 0.165.

The low friction resin composite may have a lower coefficient of friction under lubricating conditions to which conventional lubricants are applied. Here, the type and application method of the lubricant are not particularly limited.

Specifically, the low friction resin composite is a thrust washer specimen having a contact area of 1.3 cm ² based on the frictional carbon steel under the condition that the PV value is 4.6 MPa · m / s based on the ASTM D3702 standard. The coefficient of friction in the lubrication (lubricant: automotive lubricant) conditions measured for may be 0.060 or less.

Specifically, the friction coefficient under the lubrication conditions may be 0.060 or less, or 0.057 or less, or 0.055 or less. Preferably, the friction coefficient may be 0.035 to 0.060, or 0.040 to 0.060, or 0.040 to 0.057, or 0.045 to 0.057, or 0.045 to 0.055.

When measuring the friction coefficient, the condition of PV value of 2.3 MPa · m / s can be realized by the pressure (P) of 1.63 MPa and the rotational speed (V) of 1.41 m / s, and the PV value of 4.6 MPa · m / s. The condition of s can be realized by a pressure P of 1.63 MPa and a rotational speed V of 2.82 m / s.

On the other hand, the low friction resin composite may have a processing temperature in the range of 150 to 350 ℃.

The processing temperature means a temperature at which the low friction resin composite exists in a processable state. The processing temperature may be, for example, a melting temperature (Tm) or a glass transition temperature (Tg).

The process window of the low friction resin composite, that is, the absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) of the phthalonitrile compound and the curing agent is 30 ° C or more, 50 ° C or more, or It may be at least 100 ℃. The curing temperature Tc may be higher than the processing temperature Tp. Such a range may be advantageous to secure appropriate processability in the process of producing a material for counter friction parts, for example, using the polymerizable composition. The upper limit of the process window is not particularly limited. For example, the absolute value of the difference (Tc-Tp) between the processing temperature Tp and the curing temperature Tc may be 400 ° C or less or 300 ° C or less.

On the other hand, the low friction resin composite may be provided in a prepolymer state.

The prepolymer state is a state in which a reaction between the phthalonitrile compound constituting the binder and a curing agent occurs to some extent (for example, a state in which polymerization at the so-called A or B stage stage has occurred), but not attained a fully polymerized state. It can mean a state that can be processed by showing the proper fluidity without.

As a non-limiting example, the prepolymer state has a melt viscosity of 10 Pa.s to 100,000 Pa.s, 10 Pa.s to 10,000 Pa.s, or 10 Pa.s to 5,000, measured at a temperature in the range of 150 to 250 ° C. It may mean a state within the range of Pa · s.

For example, the processing temperature of the prepolymer may be in the range of 150 to 350 ℃. In this case, the processing temperature means a temperature at which the prepolymer exists in a processable state.

II. Material for counter friction part

According to another embodiment of the present invention, there is provided a material for counter friction parts manufactured using the low friction resin composite.

As described above, the low friction resin composite enables to provide a material for relative friction parts having durability and low friction characteristics even in an ultrahigh pressure and ultra high speed environment.

Examples of the material for counter friction parts include bearings, bushings, thrust washers, oil seals, piston rings, sliding, rollers, and the like. The relative friction component material may be applied to automobiles, aircrafts, and other industrial materials.

The relative friction component material may be manufactured by heating the prepolymer of the low friction resin composite to form a desired shape and then curing it. Processing and curing methods for the production of the material for the frictional component may be performed according to a known method.

The low friction resin composite according to the present invention has excellent heat resistance and a low coefficient of friction, thereby making it possible to provide a material for relative friction parts having excellent durability and low friction characteristics.

1 is an exploded perspective view of a friction coefficient measuring device for measuring a friction coefficient according to ASTM D3702 standard.

2 to 4 show ¹ H-NMR data for the compounds according to Preparation Examples 1 to 3, respectively.

Hereinafter, preferred embodiments will be presented to aid in understanding the present invention. However, the following examples are only for illustrating the invention, and the present invention is not limited thereto.

^One Nuclear Magnetic Resonance (H-NMR) Analysis

NMR analysis of the compounds prepared below was performed according to the manufacturer's manual using Agilent's 500 MHz NMR equipment. Samples for NMR measurements were prepared by dissolving the compound in dimethyl sulfoxide (dSO) -d6.

Preparation Example 1 Synthesis of Phtharonitrile Compound (PN1)

Compound (PN1) of formula (A1) was synthesized by the following method.

32.7 g of the compound of Formula A2 and 120 g of dimethyl formamide (DMF) were added to a three neck round bottom flask (RBF), and stirred at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula A3 was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. Thereafter, the filtered reaction was dried in a vacuum oven at 100 ° C. for 1 day, and after removing water and residual solvent, the compound of formula A1 (PN1) was obtained in a yield of about 80% by weight. ¹ H-NMR analysis of the obtained compound of formula A1 (PN1) is shown in FIG. 2.

[Formula A1]

[Formula A2]

[Formula A3]

Preparation Example 2 Synthesis of Curing Agent Compound (CA1)

Compound (CA1) of Formula A14 was synthesized by dehydration of diamine and dianhydride. 24 g of 4,4'-oxydianiline (4,4'-oxydianiline) and 40 g of N-methyl-pyrrolidone (NMP) were added to a three neck round bottom flask (RBF), followed by stirring at room temperature to dissolve. . The water was cooled in a water bath, and 8.7 g of the compound of Formula A15 was slowly added in three portions and 40 g of NMP was added thereto. When all the compound added dissolved, 16 g of toluene was added to the reaction for azeotrope. Dean-Stark device and reflux condenser were installed, and toluene was charged to Dean-Stark device. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 ° C, and stirred for 3 hours. Water generated while the imide ring was formed was further stirred for 2 hours while being removed by the Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature and recovered by precipitation in methanol. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven to yield compound (CA1) of formula A14 in a yield of about 85% by weight. ¹ H-NMR analysis of the obtained compound of Formula A14 (CA1) is shown in FIG. 3.

Formula A14

[Formula A15]

Preparation Example 3 Synthesis of Curing Agent Compound (CA2)

The compound of formula A18 (CA2) was synthesized by dehydration of diamine and dianhydride. 8.1 g of the compound of Formula A16 (m-phenylene diamine) and 50 g of NMP (N-methylpyrrolidone) were added to a three neck round bottom flask (RBF), and the mixture was stirred at room temperature to dissolve. The above was cooled by a water bath, and 26 g of the compound of Formula A17 was gradually divided into three portions and added with 60 g of NMP. When all the added compound was dissolved, 23 g of toluene was added to the reactant for the azeotrope reaction. Dean Stark unit and reflux condenser were installed, and toluene was charged to Dean Stark unit. 5.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 ° C, and stirred for 3 hours. Water generated as the imide ring was formed was further stirred for 2 hours while the Dean Stark apparatus was removed, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature and recovered by precipitation in methanol. The recovered precipitate was soxhlet extracted with methanol to remove the remaining reactants and dried in a vacuum oven to give compound A18 (CA2) in a yield of about 93% by weight. ¹ H-NMR analysis of the obtained compound of formula A18 (CA2) is shown in FIG. 4.

[Formula A16]

Formula A17

Formula A18

In Formula A18, n is about 3.

Example 1

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

21.4 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle diameter of 100 μm or less), 14.2 parts by weight of tungsten disulfide (WS ₂ , manufacturer: Zerofriction, particle size of 800 nm), and 7.14 parts by weight of polytetra with respect to 100 parts by weight of the binder. Fluoroethylene (PTFE, manufacturer: DuPont, particle size 4㎛) was added and then mixed well to prepare a resin composite.

Example 2

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

21.4 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle size of 100 μm or less), 7.1 parts by weight of molybdenum disulfide (MoS ₂ , manufactured by Sigma-Aldrich, particle size of 2 μm), and 14.2 parts by weight, based on 100 parts by weight of the binder. Resin composite was prepared by adding pulverized carbon fibers (mCF, manufacturer: Zoltek, 100 μm in length) and then mixing well.

Example 3

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

23.1 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle size of 100 μm or less), 15.4 parts by weight of tungsten disulfide (WS ₂ , manufacturer: Zerofriction, particle size of 800 nm), and 15.4 parts by weight of polytetra with respect to 100 parts by weight of the binder. Fluoroethylene (PTFE, manufacturer: DuPont, particle size 4㎛) was added and then mixed well to prepare a resin composite.

Comparative Example 1

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

17.6 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle size of 100 μm or less) was added to 100 parts by weight of the binder, followed by mixing well to prepare a resin composite.

Comparative Example 2

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

20.0 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle size of 100 μm or less) and 13.3 parts by weight of polytetrafluoroethylene (PTFE, manufacturer: DuPont, particle size of 4 μm) were added to 100 parts by weight of the binder. Mixing produced a resin composite.

Comparative Example 3

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

To 100 parts by weight of the binder, 20.0 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle diameter of 100 μm or less) and 13.3 parts by weight of tungsten disulfide (WS ₂ , manufacturer: Zerofriction, particle size 800 nm) were added and mixed well. Resin composites were prepared.

Comparative Example 4

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

To 18 parts by weight of the binder, 18.8 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle size of 100 μm or less) and 6.3 parts by weight of molybdenum disulfide (MoS ₂ , manufactured by Sigma-Aldrich, particle size of 2 μm) were added well. Mixing produced a resin composite.

Comparative Example 5

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

To 100 parts by weight of the binder, 20.0 parts by weight of graphite (manufacturer: Samchun chemicals, powder having a particle diameter of 100 μm or less) and 13.3 parts by weight of pulverized carbon fiber (mCF, manufacturer: Zoltek, length 100 μm) were added and mixed well. Resin composites were prepared.

Comparative Example 6

Vespel SP-21, a low friction grade product from DuPont, was obtained and used commercially. The Vespel SP-21 is known to contain 15% by weight of graphite (17.6 parts by weight of graphite based on 100 parts by weight of PI resin) in the polyimide resin.

Comparative Example 7

A low friction grade product from Victrex, PEEK 450FC30, was obtained and used commercially. The PEEK 450FC30 is known to contain 30 parts by weight of a filler (a mixture of carbon fiber, graphite and PTFE) based on 100 parts by weight of PolyEtherEtherKetone resin.

Reference Example 1

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

21.4 parts by weight of molybdenum disulfide (MoS ₂ , manufactured by Sigma-Aldrich, particle size 2 μm), 14.2 parts by weight of tungsten disulfide (WS ₂ , manufactured by Zerofriction, particle size 800 nm), and 7.14 parts by weight of the binder Polytetrafluoroethylene (PTFE, manufacturer: DuPont, particle size 4㎛) was added and then mixed well to prepare a resin composite.

Reference Example 2

A binder was prepared by mixing 100 parts by weight of Compound (PN1) of Preparation Example 1 and about 0.18 mole of Compound (CA1) of Preparation Example 3 with respect to 1 mol of Compound (PN1).

21.4 parts by weight of pulverized carbon fiber (mCF, manufactured by Zoltek, 100 μm in length), 14.2 parts by weight of tungsten disulfide (WS ₂ , manufactured by Zerofriction, particle size 800 nm), and 7.14 parts by weight of polytetra Fluoroethylene (PTFE, manufacturer: DuPont, particle size 4㎛) was added and then mixed well to prepare a resin composite.

Test Example

Each of the resin composites prepared in Examples and Comparative Examples was melted at 240 ° C. and stirred for 5 minutes to prepare a prepolymer.

The prepolymer was placed in a mold and melted, and then cured under conditions of 2 hours at 200 ° C., 2 hours at 250 ° C., 2 hours at 300 ° C., and 2 hours at 350 ° C., to provide a thrust washer specimen according to ASTM D3702. Was prepared. The products of Comparative Examples 5 and 6 were cut to produce thrust washer specimens in accordance with ASTM D3702 standards.

S45C was prepared as a counterpart carbon steel. S45C is a mechanical structural carbon steel which is a steel material containing 0.45% of carbon according to JIS G4053.

A coefficient of friction and wear rate were measured for the specimens according to ASTM D3702 standard using a coefficient of friction meter (TE 92, manufactured by Phoenix). The results are shown in Tables 1 and 2 below.

PV Value 1: 2.3 MPam / s (Pressure (P): 1.63 MPa (16 bar, 220 N), Rotational speed (V): 1.41 m / s (1000 rpm))

PV Value 2: 4.6 MPam / s (Pressure (P): 1.63 MPa (16 bar, 220 N), Rotational speed (V): 2.82 m / s (1000 rpm))

-Time: 1200 s

Unlubricated conditions

-Lubricated conditions (Car lubricant, vendor: HYUNDAI MOBIS, product name: ATF SP-III)

Referring to Table 1, it is confirmed that the specimens according to Examples 1 to 3 exhibited a lower friction coefficient or lower wear rate than the specimens of Comparative Examples 1 to 5.

In particular, as confirmed through Examples 1, 3 and Comparative Example 3, when graphite and tungsten disulfide were applied as the filler, friction properties were remarkably improved when polytetrafluoroethylene was applied together.

And, as confirmed through Example 2 and Comparative Example 4, when graphite and molybdenum disulfide were applied as the filler, the friction properties were remarkably improved when the pulverized carbon fibers were applied together.

Claims (15)

1. A binder containing a phthalonitrile resin and

   3 or more fillers dispersed on the binder

   Containing, low friction resin composite.
2. The method of claim 1,

   The filler is a low friction resin composite, at least three additives selected from the group consisting of graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and pulverized carbon fibers.
3. The method of claim 2,

   The filler comprises graphite,

   The filler further comprises at least two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and ground carbon fiber, low friction resin composite.
4. The method of claim 1,

   The filler is a low friction resin composite, a powdery additive having a longest diameter of 0.01 to 100 ㎛.
5. The method of claim 1,

   100 parts by weight of the binder including the phthalonitrile-based resin and

   1 to 100 parts by weight of the filler

   Containing, low friction resin composite.
6. The method of claim 3, wherein

   100 parts by weight of the binder including the phthalonitrile-based resin;

   15 to 30 parts by weight of graphite;

   10 to 40 parts by weight of two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and ground carbon fiber

   Containing, low friction resin composite.
7. The method of claim 1,

   The binder including the phthalonitrile-based resin is a low friction, wherein the composition containing the phthalonitrile compound is cured by at least one curing agent selected from the group consisting of amine compounds, hydroxy compounds and imide compounds Resin composite.
8. The method of claim 7, wherein

   The phthalonitrile compound is a compound represented by the following formula P1, low friction resin composite:

   [Formula P1]

   

   In formula P1, R R ^P11 to ^P16 each independently represent a hydrogen, an alkoxy group of the alkyl group, C _1-5 of C _1-5, an aryl group, a group the formula P2, P3 or the formula a group of C _6-30 , At least two of R ^P11 to R ^P16 may be represented by the following Chemical Formula P2 group or Chemical Formula P3 group,

   [Formula P2]

   

   In Chemical Formula P2,

   L ^P2 is a direct bond, an alkylene group of C _1-5 , -O-, -S-, -C (= 0)-, -S (= 0)-, or -S (= 0) _2- ,

   R R ^P21 to ^P25 are two or more of each independently represent a hydrogen, an alkoxy group, an aryl group, a cyano group, a C _6-30 alkyl group a, C _1-5 of C _1-5, the R R ^P21 to ^P25 is a cyano group to be,

   [Formula P3]

   

   In Chemical Formula P3,

   L ^P3 is a direct bond, an alkylene group of C _1-5 , -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) _2- , -C ( CH ₃ ) _2- , -C (CF ₃ ) _2- , or -C (= 0) NH-,

   R R ^P31 to ^P35 are each independently a hydrogen, an alkyl group, an alkoxy group, an aryl group, the P2 group of the formula C _6-30 of C _1-5, and one or more of the R R ^P31 to ^P35 of the C _1-5 is The above formula is P2 group.
9. The method of claim 6,

   The hardener is an imide compound represented by the following formula (9), low friction resin composite:

   [Formula 9]

   

   In Chemical Formula 9,

   M is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound,

   X ¹ and X ² are each independently a divalent radical derived from an alkylene group, an alkylidene group, or an aromatic compound,

   n is a number of 1 or more.
10. The method of claim 9,

    In Formula 9, M is a tetravalent radical derived from alkanes, alkenes, or alkynes, or a tetravalent radical derived from a compound represented by any one of the following Formulas 10 to 15:

    [Formula 10]

    

    In Formula 10, R ¹⁰¹ to R ¹⁰⁶ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group;

    [Formula 11]

    

    In Formula 11, R ¹¹¹ to R ¹¹⁸ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group;

    [Formula 12]

    

    In Chemical Formula 12,

    R ¹²⁰ to R ¹²⁹ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group,

    X is a single bond, an alkylene group, an alkylidene group, -O-, -S-, -C (= O)-, -S (= O)-, -S (= O) _2- , -C (= O ) -OL ¹ -OC (= O)-, -L ² -C (= O) -OL ^3- , -L ⁴ -OC (= O) -L ^5- , or -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ^8- , wherein L ¹ to L ⁸ are each independently a single bond, -O-, an alkylene group, or an alkylidene group, and Ar ¹ and Ar ² are each independently an arylene group;

    [Formula 13]

    

    In Chemical Formula 13,

    R ¹³¹ to R ¹³⁴ are each independently hydrogen, an alkyl group, or an alkoxy group, two of R ¹³¹ to R ¹³⁴ may be connected to each other to form an alkylene group,

    A is an alkylene group or alkenylene group, wherein the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom;

    [Formula 14]

    

    In Chemical Formula 14,

    R ¹⁴¹ to R ¹⁴⁴ are each independently hydrogen, an alkyl group, or an alkoxy group,

    A is an alkylene group;

    [Formula 15]

    

    In Chemical Formula 15,

    R ¹⁵⁰ to R ¹⁵⁹ are each independently hydrogen, an alkyl group, or an alkoxy group.
11. The method of claim 9,

    N in the formula 9 is a number in the range of 2 to 200, low friction resin composite.
12. The method of claim 1,

    No lubrication (self lubrication) measured on thrust washer specimens with a contact area of 1.3 cm ² , based on the frictional carbon steel, in accordance with ASTM D3702, under a PV value of 2.3 MPa · m / s. The low friction resin composite having a coefficient of friction of 0.175 or less under the conditions.
13. The method of claim 1,

    Lubrication measured on thrust washer specimens with a contact area of 1.3 cm ² , based on the friction material carbon steel, in accordance with ASTM D3702, with a PV value of 4.6 MPa · m / s. A low friction resin composite having a coefficient of friction of 0.060 or less under lubricating oil) conditions.
14. A material for counter friction parts manufactured using the low friction resin composite of claim 1.
15. The method of claim 14,

    The relative friction component material is a bearing, a bushing, a thrust washer, an oil seal, a piston ring, sliding (sliding), or a roller, material for a relative friction component.

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